PROCEEDINGS OF THE CHEMICAL SOCIETY DECEMBER 1962 AN INTERNATIONAL SYMPOSIUM ON CARBOHYDRATE CHEMISTRY Organised by the University of Birmingham and the Chemical Society AN INTERNATIONAL on SYMPOSIUM Carbohydrate Chemistry was held at the University of Birmingham from July 16th to 20th 1962. The Symposium com- memorated the life and work of the late Sir Norman Haworth after whom the newly opened laboratories of the Chemistry Department of the University have been named. Appropriately the meetings were opened by Professor M. Stacey in the lecture theatre of the new building which constitutes the third extension to the Department since Haworth’s arrival in 1925. Commemorative lectures reviewing Sir Norman’s life and work were given by Professor E.L. Hirst and Professor Stacey both of whom were associated with him for so long. Professor Hirst gave a broad survey of some of the landmarks in carbohydrate chemistry with which Sir Norman was concerned as well as some of the lesser known chapters of the story. The audience heard with great interest a vivid account of a meeting in Li&ge in 1930 between Haworth C. S. Hudson C. B. Purves and E. L. Hirst. During the Tenth Con- ference of the International Union of Chemistry in Likge two different structures had been put forward for methyl a-D-mannoside. At the subsequent private meeting the apparent contradiction was resolved and the foundation laid for much work which followed over the whole field of carbohydrate chemistry.Structures of glycosides such as this are now accepted often with little thought for the difficulties encountered in their establishment and it was a stimulating experience to be taken back into the pioneering days of monosaccharide chemistry. One was also impressed by the forward thinking of those early days when techniques were being initiated such as optical rotatory dispersion which are still today the subject of intensive investigation. During the Symposium over forty invited papers were delivered and it is impossible in a brief sum- mary to mention more than a very few. No general survey is possible of a symposium which covered all aspects of such a wide subject and the writer will confine himself to a few of the papers which seem to characterise various aspects of the Symposium as a whole.New powerful techniques for the study of poly-saccharides were discussed by Professor F. Smith who was also associated with Haworth for many years. By the use of periodate oxidation followed by reduction and hydrolysis of the cyclic forms of the so-called dialdehydes produced a number of pro b- lems have become capable of solution which proved refractory with earlier techniques. Thus it is now possible to recognise one branch point in one hundred and fifty residues in amylose and it appears also that 1+3 linkages in glycogen can now be excluded. Methylation which has played such a prominent part in the determination of carbohydrate structures was reviewed by Professor Richard Kuhn and it is noteworthy that the introduction of NN-dimethyl- formamide as solvent in methylations with methyl iodide should facilitate in one operation complete methylation of materials which are methylated only with difficulty by other methods.373 A number of papers dealt with various biochemical aspects of carbohydrate chemistry. Professor W.T. J. Morgan very clearly reviewed present knowledge of mucopolysaccharides associated with blood-group specificity. Dr. Kabat while emphasising the various pitfalls which exist linked immunological studies with structural determination a further example be- ing provided by Dr. M. Heidelberger. The close inter- relationships of structural and biological studies were most forcibly illustrated by Professor Westphal.He described how “rough” bacterial strains contain polysaccharides possessing the same main structures but lacking the side chains characteristic of the materials from corresponding “smooth” forms. Professor Wallenfels discussed the influence of the structure of relatively simple substrates on the rate of hydrolysis of /3-galactosidase and related this to the mode of interaction between enzyme and sub-strate. With enzymes necessitating the use of com- plex polysaccharide substrates the same approach is not feasible but by ingenious modifications of the structures of amylose Schardinger dextrins and other complex materials Dr. Whelan showed how it may be possible in future to investigate the points of attachment between these materials and the appropri- ate carbohydrases.Viewed in the light of Haworth’s work on poly- saccharides the papers presented at the Symposium of which those mentioned above are but a few illustrated clearly the way in which the subject has developed in the short time since his death. On the one hand new organic techniques are being developed and used for the study of the more intimate details of polysaccharide structure while on the other hand chemical arguments are now being sup-plemented by biochemical and biological contribu- tions to the study of structure and function. Some problems which proved intractable in Haworth’s day are still yielding only very little to attack. Sulphated polysaccharides for instance may be mentioned in this connection.Dr. Elizabeth Percival described a very promising new approach to the problem of the removal of sulphate residues but it seems that in this field new techniques are not keeping pace with the number of new materials of high biological importance. In the monosaocharide field too new structural PROCEEDINGS types are being studied as illustrated by Dr. A. B. Foster’s paper on carbohydrate components of anti- biotics and Professor Overend’s discussion of branched-chain sugars. Great advances are also be-ing made in the understanding of the chemistry of the simpler saccharides. Professor Angyal’s contribu- tion on quantitative conformation analysis under- lined the importance of the stereochemical approach to problems both of structure and reactivity.The latter aspect was also well illustrated by Dr. B. R. Baker and Dr. J. G. Buchanan both of whom dis- cussed neighbouring-group effects. Dr. H. S. Isbell took the consideration of conformation a stage further in his paper on the oxidation of aldoses with bromine. Thus he showed that the half-chair con- formation of the transition state in the oxidation is more readily formed from a reacting molecule in which the anomeric hydroxyl group occupies an equatorial rather than an axial position. Undoubted- ly the study of conformation will develop very rapidly with the advent of nuclear magnetic reson- ance spectroscopy. Dr. Wolfrom described how in a particular instance a structural problem of long standing had been quickly solved by the use of this technique and it was abundantly clear from the paper by Dr.Lemieux on the synthesis of a-and /3-glycosides what advantages can accrue from its routine application. Some may as yet be a little chary of accepting all conclusions drawn from this method but there can be no doubt that the develop- ment of structural studies will be greatly influenced by the use of physical techniques which as men- tioned above Haworth did so much to encourage. The occasion of this Symposium was a most appropriate opportunity to review all the branches of carbohydrate chemistry. Its success can be measured by the fact that it drew nearly three hundred participants from twenty countries. The organisers of the meetings are to be congratulated on providing a programme with so much of interest for workers in all branches of the field.Not the least important aspect of the meetings was the social part of the programme which did a great deal to foster not only the enjoyment but also the scientific value of the Symposium. The writer for one looks forward at an appropriate time to another symposium on carbohydrate chemistry as useful and as enjoyable. G.R.BARKER. DECEMBER 1962 375 SYMPOSIUM ON THE CHEMISTRY OF THE EARLY TRANSITION ELEMENTS THISsymposium the scientific programme of which had been arranged by Professor R. S.Nyholm took place in the Chemistry Department University Col- lege London on Thursday October 25th 1962. The attendance at this meeting was encouragingly large certainly indicating contemporary interest in these elements; especially welcome was the evidence of particular interest in second and third row elements.These elements have been the objects of useful re- search for but a comparatively short time owing to the inherent manipulative difficulties involved in dealing with their compounds. Now that the in- organic chemist’s fears of dry-box and vacuum tech- niques are passing there is little doubt that deriva- tives of the early transition metals will prove of con-siderable value in extending our theoretical know- ledge of transition metal chemistry. In the unavoidable absence of Professor Nyholm Dr. M. L. Tobe (University College London) acted as Chairman of the first session and presented a short introductory paper.Dr. Tobe first pointed out some of the reasons for the paucity of information about the early transition elements and indicated that with the development of new techniques for handling un- stable materials and particularly the application of new solvent systems many difficulties had been over- come. He then discussed the main factors which determine the differences between the properties of early and late transition elements. The first factor arises from the relatively inefficient shielding power of electrons in d orbitals. Hence along the series do4dlO the electrons are unable to compensate for the increase in nuclear charge. This is reflected in a marked increase in the ionisation potentials along such a series and an increase in electronegativities.The change in electronegativity is responsible for the preference of the Iater transition metals for polarisable ligands (e.g.,I- CN- tertiary phosphines and arsines etc.) while the early transition metals have much stronger affinities for electronegative ligands such as F-and oxygen containing groups. Secondly since the early transition elements have few d electrons even in their lowest oxidation states there is a strong probability of the formation of com-plexes of high co-ordination number. In complexes where the bonding is essentially covalent there ap- pears to be a strong tendency for occupation of all nine available orbitals (five nd one (n+l)s and three (n+l)p) by either non-bonding or bonding electrons e.g.Mo(CN);- Mo(CN):-. Lastly as a consequence of this tendency to high co-ordination number one finds compounds of simple stoicheio- metry to have unusual structures. For example the compound MoCl has a structure based upon the unit [Mo,Cl,]*+. Thus by forming multi-centre bonds the metal can effectively increase its co-ordination number. The Chairman then introduced Professor C. J. Ballhausen (Copenhagen) who read a paper entitled %-Bonding in Distorted Octahedral Complexes.” For tetragonal distorted octahedral complexes the principal question is the distribution of the dn-orbitals among the ligands. Examination of vanadyl complexes by optical and electron spin resonance spectroscopy and consideration of bond distances indicates considerable d,,-p contribution to the metal-oxygen bond.As a result of these studies a “Golden Rule,” that in distorted octahedral com-plexes all .ir-bonding is axially directed has been formulated. For chromium(1n) complexes the “Golden Rule’’ would predict that the visible absorp- tions of Cr(CN),(N0)3- and of Cr(H20),(N0)2+ should be identical if the Cr-(NO) bond determines the overall bonding. Experimentally this conjunction is seen to hold. Mossbauer-effect measurements of Fe(CN),(N0)2- also indicate that the thesis is correct. Professor F. Fairbrother (Manchester) then pre- sented a paper entitled “The Chemistry of Niobium and Tantalum,” which dealt with the pentahalides of these metals and particularly with the complexes which they form with ligands containing oxygen and sulphur donor atoms.NbCI, TaCl, NbBr, and TaBr form 1:1 complexes with diethyl ether which are solid crystalline compounds with low dissociation pressures and which decompose at about 100” into ethyl halide and metal oxytrihalide. With tetrahydro- furan at room temperature the ring is opened and polymerisation occurs. On the other hand these halides which also form 1:1 adducts with dimethyl and diethyl sulphides (in which they are more soluble than in ether) form 1:2 complexes with tetrahydro- thiophen which are insoluble in excess of the ligand. TaI, which does not appear to possess any significant Friedel-Crafts type of catalytic activity does not form a complex with ether but does so with diethyl sulphide in which it is also rather more soluble than in ether.The smaller dissociation pressures of the sulphide complexes suggests that the metal-sulphur bond is stronger than the metal-oxygen bond. This has been confirmed by a displacement reaction EtzS will dis- place the whole of the ether from Et20,NbCl, but the ether will not displace the sulphide from the sulphide complex. Similarly with the pentafluorides which form 1:2 and 1:1 adducts with dimethyl ether but only 1:1 complexes with diethyl ether and with dimethyl and diethyl sulphides ;the variation with temperature of the dissociation pressures shows that the sulphur complexes are the stronger. In all cases the heats of formation of the niobium complexes are somewhat greater than those of the tantalum complexes.This work has also been extended to include the reactions of the pentachlorides and pentabromides with dimethyl sulphoxide. Here a more complicated reaction is involved the pentahalide undergoing a partial solvolysis followed by oxygen bridging to form a dimer trimer or tetramer to which addi- tional molecules of sulphoxide are co-ordinated. A paper “Some Complexes of the Group VA Nitrates,” by K. W. Bagnall and P. J. Jones was then read by Dr. K. W. Bagnall (Harwell). It was pointed out that although the vanadium nitrates V02N0 and VO(NO,) have been reported there is no record of any niobium tantalum or protactinium ana- logues.Niobium pentachloride forms complexes with amines diethyl ether and phosphorus oxy- chloride none of which is a suitable non-aqueous solvent for the preparation of the nitrate but the pentachloride is found to be quite soluble in methyl cyanide NN-dimethylacetamide and ethyl acetate and less soluble in nitrobenzene ionising solvents which are quite suitable for the preparation of nitrates by reaction of chlorides with dinitrogen tetroxide. A complex of composition Nb02N0,,0-6MeCN has been obtained from methyl cyanide solution and this is stable at 70” and is apparently trimeric the suggested structure being (1) since the anhydrous compound takes up one molecule of water for each trimer unit in moist air so making all the niobium atoms presumably sexicovalent.The anhydrous com- pound is diamagnetic but gives a single low intensity peak in the electron spin resonance spectrum; on hydration the intensity increases tenfold and then decays with a half-time of about one day. The analogous complex with NN-dimethylacetamide is o=k-0-fa-0 -TO=O 03N’ \NO3 (n) polymeric whereas the complexes with nitrobenzene and ethyl acetate appear to be monomers and are un- stable. The tantalum oxynitrate-methyl cyanide complex prepared in the same way is more complex and may be derived from TaO(NO,),. One possible structure is (11). The last paper of this section “Alkyl Cyanide PROCEEDINGS Complexes of some Transition Elements,” was pre-sented by Dr. G. W. A. Fowles (Southampton).This paper described the products of reaction of methyl ethyl and n-propyl cyanides with halides of some early transition metals. The reactions can be summarised as follows TiX (X = C1 and Br) TiX4,2RCN 3 TiX (X = Cl and Br) TiX3,3RCN 3 ZrX4 (X = C1 and Br) -ZrX4,2RCN inert solvent VC1,,2RCN VC14 [excess of RCN -VC13,3RCN c VX (X = C1 and Br) -VX3,3RCN MoCl -MoC14,2RCN E::} -WClJRCN 2,) .+ WBrJRCN MoBr -MoBr3,3RCN The products may be considered in two groups (i) MX4,2RCN; (ii) MX3,3RCN. Examples of the first type are obtained for do dl and d2metal-ion configurations and for the second type with d’ d2 and d3configurations. On the basis of infrared spectral and molecular-weight measure ments the first type are characterised as having trans-octahedral structures.Magnetic susceptibility and visible and ultraviolet spectra have been measured for all the compounds. Where the metal was reduced to a lower valency state with excess of cyanide attempts were made to identify the oxidation products. The cyanide complexes are valuable starting materials for the preparation of other complexes of the metals. For example MoC14,2RCN + 2L -MoCI,L + 2RCN where L = py. IPPn, AsPh,. A brief discussion of these papers then took place. Dr. P. G. Owston (Imperial Chemical Industries Ltd. Welwyn) considered that the recently deter- mined structure of ReO(PPh,),CI was in keeping with the “Golden Rule.” The structure known to be based on a distorted octahedron shows a very short Re-0 bond in one of the axial positions while the metal-ligand bonds in distorted positions about the central plain cis to the oxygen are unusually long.Some discussion was provoked by Dr. Bagnall’s paper; in particular concerning the positions of infrared bands produced by Nb=O vibrations. A suggestion that a band at -900 cm.-l was due to bridging oxygen atoms was considered to be untrue and as was pointed out in a timely comment from DECEMBER 1962 Professor J. Lewis (Manchester) the exact position of Nb= 0 stretching frequency would vary owing to vibrational interactions. Dr. J. S. Anderson (National Chemical Labora- tory Teddington) who acted as Chairman for the second session of the meeting called upon Dr.R. J. H. Clark (University College London) to deliver his paper “Higher Co-ordination Numbers of the Early Transition Elements.” Dr. Clark first re-viewed the possible stereochemistries for discrete eight-co-ordination. The number of reliably authen- ticated examples of dodecahedra1 (D,&)and of square antiprismatic (Ddd)structures are quite similar and hence it appears that there can be little energetically to choose between the two structures. Particular mention was made of the recently determined struc- ture for the compound TiC1,,2Diarsine which is the first example of eight-co-ordinated titanium. The analogous vanadium zirconium and hafnium deri- vatives are issstructural with this compound. It is evident that the steric effects of high co-ordination numbers in the first transition series are not as for- bidding as had been supposed previously but from a study of metal-halogen stretching frequencies of this series of compounds and of the isomorphous TiBr4,2Diarsine it appears that in the latter steric effects are becoming important.The possible stereochemistries for seven-co-ordina- tion were discussed and evidence presented to indi- cate that in the compounds [M2Diarsine(CO),X]X’ (M = Cr Mo W; X = Br; I; X = Br- Br3-; I- Is-) and [MDiarsine(CO),X,] (M = Mo W; X = Br I) the metal atom attains seven-co-ordination. Dr. R. Colton (Harwell) then presented a paper “Some Halogen Compounds of Technetium and Rhenium.” Until recently the only known binary halide of technetium was the tetrachloride.Recently technetium hexafluoride and technetium hexa-chloride have been prepared. The latter is made by the direct action of a stream of chlorine on the heated metal. It is very unstable and decomposes to the tetrachloride. The actions of oxygen on technetium tetrachloride and chlorine on technetium oxides have been investigated and have led to the preparation of technetium oxide chlorides. The preparation of technetium hexachloride leads to the unusual situation of a second-row transition metal technetium showing a higher covalency in its chlorides than the corresponding third-row metal since the pentachloride was the highest known chloride of rhenium. A search was made for rhenium hexachloride and a study of the reaction between rhenium powder and chlorine showed that the hexa- chloride is always formed together with the penta- chloride.Using a film of freshly reduced rhenium metal instead of the powder gave the hexachloride exclusively. Bromine vapour reacts slowly with technetium metal. Rhenium powder reacts readily with bromine to give the blue pentabromide which can be thermally decomposed in nitrogen to give the tribromide. There is no evidence of the formation of rhenium hexabromide when a film of the freshly reduced metal is treated with bromine vapour. Oxide bromides of technetium and rhenium have been prepared by the action of bromine on the metal oxides. A paper “Fluorine Compounds of the Chromium Group” was read by Dr.R. D. Peacock (Birming- ham). Of the four fluorides of chromium the least well known is the pentafluoride CrF5. This the highest fluoride was first prepared by Wartenberg in 1940 and is a red volatile material with a paramagnetism corresponding to one unpaired electron. Vapour- pressure studies show the existence of two solid phases. Molybdenum forms four fluorides X-Ray investi- gations of the solid pentafluoride show that the structural unit is a tetramer with the metal atoms at the corners of a square linked together by linearly bonded bridging fluorine atoms. The same type of structure appears to be adopted by other transition- metal pentafluorides. Finally although somewhat divorced from the transition metals Dr. Peacock announced that he had with him a sample of the newly prepared XeF,.This was to be gazed upon with wonder at the end of the proceedings. The final paper of the symposium “Stability of Bivalent and Tervalent Metal Complexes from Calcium to Iron,” was read by Dr. R. J. P. Williams (Oxford). Some stability data were given for the cations Cr(II) V(II) Ti@) and VO(rv). The most noteworthy feature of the data is the absence of a general pattern of stability constants from Ca(n) to Mn(II) or from Sc(n~) to Fe(rrr) such as has been found in the series Mn(I1) to Zn(rr). Furthermore while ammine complexes are amongst the most stable in the later parts of transition series they are of much less stability in the first part of the transition series where pride of place goes to RO-ligands such as oxide hydroxide enolate and phenolate.Spin- pairing affects stabilities in only one known case but polymerisation is often observed. The chemistry of solutions of Ti(m) is quite extra- ordinary. The step constants for the oxalato and fluoride complexes are extremely irregular. The spectra of the compounds are difficult to interpret as the splittings are frequently unexpectedly large. A cation with a single d electron does not behave in a manner similar to one with six d electrons,e.g.,Fe(rr). The chemistry of vanadyl is not very similar to that of other bivalent cations. Comparison with the chem- istry of uranyl indicates that this is due to a high effective value of charge/radius ratio. Perhaps as a result of the imminent opening of the bar final discussion was rather brief.The purity of rhenium from various sources was one subject of interesting discussion. From the contributors’ ex- periences it appears that this is an important factor in determining the products of halogenation. Dr. Williams mentioned some interesting spectroscopic data concerning dimethylglyoxime complexes which appeared to him to be evidence for some degree of v-bonding in directions other than that demanded by Professor Ballhausen’s “Golden Rule.” On conclusion of this successful meeting one of the Honorary Secretaries of the Society Professor K.W.Sykes offered a formal vote of thanks to the organisers chairmen and authors. On reflection it is clear that the real value of this meeting will be evident if more thoughts about these PROCEEDINGS elements have been stimulated and more experi- mental and theoretical work encouraged.It is almost certain for example that more work will show that at least for the second and third row elements com- plexes in which the metal has a high co-ordination are quite commonplace. It is evident that more physical data are required and now that it appears that preparative methods and handling techniques are not impossibly difficult such data will no doubt be available soon. One aspect of the chemistry of these elements which has been neglected (with the exception of those of the first row) is the stabilisation of low oxidation states. This is without doubt a very difficult problem but with the gathering body of knowledge of the factors which determine the stability of a particular oxidation state should not prove impossible with careful choice of specifically designed ligands.M. H. B. STIDDARD. LETTER TO THE EDITOR Dear Sir THEFORBES MYSTILLERY THEarticle onThe Evolution of The Still by Professor R. J. Forbes printed in Proceedings 1962 p. 238 is ably illustrated with reproductions of early drawings not otherwise readily available to the historical research worker and is typical of his well-known publications on early history of technology. However the historical literature of this field has many imperfections and I should like here to prevent one more misinterpretation.Professor Forbes wrote “Steam-heating in closed coils was used until Savalle’s regulator of 1857 made the use of live steam during distillation possible.” There is no doubt however that steam-heating in closed coils was used before 1857 and that live steam was also used. As an example of this one finds in the Reports of the Juries Vol. 11 of the Great Exhibition of 1851 p. 1376 a description of the methods then in use at the famous Candle Works in Vauxhall London at that time and moreover the method was covered by British Patents taken out by George Wilson and W.&ley Jones in December 1842 from which time it had been used daily on a very large scale. By this process fats which had been decom- posed by acid were distilled “by means of steam which passes in a minute stream out of a perforated coil fixed in the bottom of the still.” Those stills held “five tons of fat” each and were made of copper.By 1851 the works referred to was distilling 130 tons of fatty oils per week using live steam and “the steam is previously heated by passing through a system of iron pipes placed in a furnace” taking the tempera- ture up to 560”~. Warren De la Rue obtained British Patent No. 1748 in July I853 for Improvements in Treating and Preparing Burmese Petroleum to obtain distillates and the process was based on the stills he had seen in use at the above Candle works before and since 1851. He specifies a “metallic or other still” the form. of which was not material “a plain cylinder answer- ing as well as any other.” The steam enters by a pipe which “proceeds to within an inch or two of the bottom of the still; here the open end of the steam pipe either terminates or ends in a perforated coil pipe supported parallel with the bottom of the still.” In one of his books on early Petroleum History Professor Forbes remarks that Warren De la Rue described his process in detail and quotes a French periodical Le Technologiste,Vol.XX issued in 1859. This would lead the uninformed to believe that the distillation with live steam for petroleum fractionat- ing started at that time and incidentally if this were true it would be confirmation of the idea that such a process only came into being after Savalle’s “regu- lator of 1857” had been invented.However Le Technologiste’sso-called description “par M. W. de La Rue” (according to the title given it) is a pirated translation of De la Rue’s British Patent of 1853 into French. The following is the French translation so far as live steam is concerned and the reader is invited to compare it with the original passage quoted above from the British Patent “Un tuyau de vapeur . . . descend jusqu’h 5 B DECEMBER 1962 6 centimktres du fond de l'alambic ob il se tennine par me pornme d'arrosoir ou un tuyau per& de trous paralellklement au fond de l'appareil." Except for the "pomme d'arrosoir" the passages are identical the French version was printed in 1859; the real date of the description was 1853. Histories that are as full of holes as were the steam coils used at the Candle works are a mystery but one wonders whether punch-card systems have been em- ployed in these modern summaries of history.Punch- cards that are full of holes in the wrong place can cause havoc but one gets a strange feeling that there is a pattern to the holes like in a pomme d'arrosoir. What one fears is a dark plot to make sure the rose is not a British Rose! Yours faithfully OWEN COLVERD. 29 Myahgah Road October 14th 1962. Mosman New South Wales Australia. COMMUNICATIONS X-Ray Investigation of the 1:1 Molecular Compound,Dinitrogen Tetroxide-l,4Dioxan By P. GROTH and 0. HASSEL DEPARTMENT BLINDERN-OSLO, (CHEMISTRY THEUNIVERSITY NORWAY) THE compound dinitrogen tetroxide-1 ,$-dioxan N2O4*C,H8O2, crystallises in triclinic crystals space group Pi.The Dirichlet's reduced unit cell containing one formula unit has the parameters at room temperature a = 5-46A; b = 6-47A; c = 6.81 A; CY = 108.5"; fl = 91-8";y = 108.4".A three-dimensional analysis has revealed the following facts Each N,04 molecule is linked to two dioxan neighburs by N-O bonds of length 2-76 A Present compound Distances N-0 1.18 A N-N 1.75 A Angl 0-N-0 135" and vice versa the structure being based on infinite chains of alternating dinitrogen tetroxide and dioxan molecules along [lll] both centrosymmetric. The distance (2.90 A) from a particular oxygen atom to the second nitrogen atom closely corresponds to the sum of the van der Waals radii of nitrogen and oxygen.The dinitrogen tetroxide molecules are planar with interatomic distances and valency angles closely cor- responding to those of the free molecule as deter- mined by electron-diffraction,1 but rather different from those reported for the solid oxide2 (see Table). The position of the dioxan-oxygen atoms is fairly well defined but the methylene groups may be in alternative positions either compatible with a Smith and Hedberg,J. Chem.Phys. 1956,25 1282. Broadley and Robertson,Nature 1949 164,915. * Davis and Hassel unpublished work. "chair" form (see Figure). The 0-0distance (2.75 A) is only slightly shorter than that found by electron diffraction (2.77 A)? Co-ordinate values for the eight half-carbon atoms with which the least-squares procedure started were obtained by using as a model the dioxan ring specified by electron-diffraction work.The R value finally arrived at using the com- plete intensity material (454 reflexions) was 0.1 1. Final statements regarding the distribution of the Free Solid N20d2 moleculef 1-1808 1.17 f0-03A 1.750 I$ 1.64 f0.03 A 133.9" 126" f 1" carbon atoms between the two sets of co-ordinates cannot yet be given. V The X-ray results are in good agreement with nuclear magnetic resonance measurements by cand. real. Bjorn Pedersen according to which a transition takes place in the solid between -30" and +lO"c. The transition may be interpreted in terms of a transition from a low-temperature frozen-in statistical distribution to a state representing a dynamic equilibrium.(Received October 22nd 1962.) PROCEEDINGS Synthesis of the Enantiomer of Natural Dolichodial By G. W. K. CAVILL and F. B. WHIT~ELD (SCHOOLOF CHEMISTRY OF NEWSOUTH WALES,KENSINGTON, THEUNIVERSITY N.S.W. AUSTRALIA) SINCE the isolation of dolichodial and related com- pounds from several species of Dolichoderine ants the structure and reactions of the natural dolichodial 0have been reported.2 A synthesis of the enantiomer of natural dolichodial analogous to the synthesis of iridodial is now described. The starting material namely ethyl D-2-cyano-6- meth yl-8,8-eth ylenedioxy oct-2-enoat e (V) results from condensation of ethyl cyanoacetate with the monoacetal (IV) that is obtained from the ethylene acetal (11)3 of D-citronellal* via the diol (111).Cyclisation of the cyanoacetate (V),with toluene-p- sulphonic acid in the presence of an excess of benzaldehyde gives the cyclopentane derivative (VI) (w) CHzw 1 &ti 61 R-M~) (VI) to2Et Et02CACN i in 80% yield. This key step would be expected to yield a mixture of the cis-(VIa) and the trans-cyclisation product (VIb).? Gas-chromatography of the product (VI) indicates that two components are present. Reduction of the mixture with sodium boro- hydride gives the cyano-alcohol (VII) (93 %) which is converted into the acrylic acid (VIIIa) (80%) on reaction with a mixture of 50% aqueous sodium hydroxide and ethylene glycol at 120".Careful methylation (diazomethane) then gives the methyl acrylate (VIIIb) (70%) A,,, (in EtOH) 212 mp (E 12,800) reduced by lithium aluminium hydride to the allylic alcohol (IX) (41 %) which on oxidation with manganese dioxide in light petroleum yields the acraldehyde (X) (58%) Amax. (in EtOH) 223 mp (E 8950). Hydrolysis with 50% aqueous acetic acid gives the dialdehyde (XI) (61 %) u 1725 1695 (C=O) 1630 (C=C) cm.-l A,,, (in H20) 223 mp (E 6850) these constants being identical with those of natural dolichodial. Gas-chromotography of our synthetic dolichodial gave two peaks of which one corresponded to that of natural dolichodial (I) and is assigned to the enantiomeric compound (XIb). The synthetic mixture of cis-and trans-isomers (XIa and b respec- tively) has been separated by preparative gas- chromatography.The infrared spectrum (liquid capillary) of the latter corresponds closely to that of the natural dolichodial (I) (the natural product con- tains a minor impurity); significant differences are noted in the 900-1300 cm.-l region of the spectrum of the cis-isomer (ma). Additional structural correlations with known cyclopentanoid monoterpenes have been undertaken. Hydrogenation (Pd-BaSO,) of the synthetic mixture (XI)yielded iridodial (XII) whose retention times(two peaks) on gas-chromatography were identical with those for iridodial synthesised from D-citronella1 by the method of Sir Robert Robinson and his col-* We thank Keith Harris and Co. Ltd.Sydney for a generous supply of D-citronellal. t The stereochemistry of the cyclisation process will be discussed elsewhere. The remaining steps (VI-XI') have been undertaken on the stereoisomeric mixture. Cavill and Hinterberger Austral. J. Chem. 1960 13 514. Cavill and Hinterberger Austral. J. Chem. 1961 14 143. a Clark Fray Jaeger and Robinson Tetrahedron 1959,6 217. DECEMBER 1962 38 1 leagues3* (however under the same conditions Finally the bis-2,4-dinitrophenylhydrazoneof the natural iridodia14 shows one equivalent and one iridodial (XII obtained on hydrogenation of the different peak). Conversion of the synthetic dolicho- synthetic dolichodial) has been converted in to dial into the nepetalinic acids of known configura-D-actinidine (XIII) (picrate m.p.145")as previously tion is in progress. de~cribed.~ (Received October lst 1962.) * This cyclisation process would yield a synthetic product which contains a mixture of cis-and trans-isomers (cf-Vla and VIb). Cavill Ford and Locksley Austral. J. Chem. 1956 9 288. Ii Cavill and Ford Austral. J. Chem. 1960 13 296. Effect of Alkali on the Reducing Species Produced in the Radiolysh of Aqueous Solutions By J. T. ALLAN M. G. ROBINSON, and G. Smom (DEPARTMENT OF CHEMISTRY KING'S COLLEGE UNIVERSITY OF DURHAM NEWCASTLE UPON % 1) IT has been suggestdl that hydrogen atoms pro- Initial yields of hydrogen on irradiation with 6oC~ duced in the radiolytic decomposition of water can y-rays of deaerated solutions of aliphatic alcohols in under alkaline conditions undergo the acid-base the presence of acetone (10%).reaction [Alcohol] [OH-] H + OH-+ (H,O)-. . . (1) (MI (MI G(H$ Propan-2-01 Reaction with hydroxyl ions was later proved by 10-2 1W6* 0.95 Jortner and Rabani2 for hydrogen atoms generated 1W2 1 o-2 0.84 externally and passed into alkaline chloroacetate 1W2 10-1 0.64 solutions. Dainton and Watt3 also invoked reaction 10-1 1o-2 0.89 (1) as one possible explanation for their observations 10-1 10-1 0.84 in irradiated alkaline nitrous oxide solutions. Ethanol We have proposed4 the existence of two reducing 1 o-2 0.93 species in the radiolysis of neutral deaerated aqueous 1o-2 1 o-2 0.74 systems. One of these readily dehydrogenates Methanol saturated organic solutes and was assumed to be a 0.92 hydrogen atom 1o-2 0.53 RH+H+R-+H .. . (2) * pH 8 (Serrensen buffer). The other solutions were made up in NaOH. We have therefore examined the effects of alkali on the hydrogen yields from deaerated solutions of some to that observed with externally generated hydrogen aliphatic alcohols in order to investigate the possi- atoms.2 They are therefore compatible with com- bility of reaction (1). These reactions were effected petition of alcohol and hydroxyl ions for the de-in the presence of acetone which in addition to hydrogenating species produced on radiolysis i.e. scavenging the negative polaron5 (the other reducing between reactions (2) and (1). Supporting evidence species formed in the primary radiolytic act) should is that the values of G(H& from equimolar (1W2~) also scavenge the product of reaction (1) (presumably solutions of the three alcohols irradiated in the also a polaron).presence of 10-2M-sodium hydroxide decrease in the The results some of which are shown in the Table order expected from the relative reactivities of these indicate that G(Ha decreases in alkaline solution alcohols to hydrogen atoms.6 and that the yields depend on the ratio of the con- We thank Professor J. J. Weiss for his encourage centrations of alcohol and hydroxyl ions (as illus-ment. trated by the propan-2-01 system) a situation similar (Received November 13th 1962.) Baxendale and Hughes 2. phys. Chem. 1958,14 323. Jortner and Rabani J. Amer. Chem. SOC.,1961 83,4868. Dainton and Watt Nature 1962 195 1294.Allan and Scholes Nature 1960 187 218. Hayon and Weiss Proc. 2nd Internat. Conf. Peaceful UsesAtomic Energy Geneva 1958 Vol. XXIX 80; Weiss, Nature 1960 186,751. Rabani J. Phys. Chem. 1962,66 361. PROCEEDINGS Proton Magnetic Resonance Spectra of 2~,4..Tri-Ocacety~-~,~~y~o-~-hexopyr a Long-rangeCoupling By L. D. HAU and I,. HOUGH (DEPARTMEW CHEMISTRY BRISTOL) OF ORGANIC THEUNIVERSITY LEMIEUXand his co-worked were unable to rationalise the acetate resonances for the 2,3,4-tri-O-acetyl-l,6-anhydrohexopyranoses, whilst the un-bridged penta-0-acetylhexopyranoses were readily analysed the signal from an axial acetoxy-methyl group being at lower field than that of an equatorial group. We have now re-examined the 60 Mc./sec.proton resonance spectra of chloroform solutions of various 2,3,4-tri-0-acetyl-1,6-anhydro-derivatives* on a Varian V 4200 B spectrometer at approximately 25O .The acetoxy-methyl resonances were interpreted by sub-dividing them into four types depending not only on their axial or equatorial disposition relative to the pyranose chair but also on their orientation above (endo) or below (exo) the plane of the pyranose ring when the 1,6-anhydro-ring is vertically above the pyranose chair. Thus equatorial substituents at C-2 and C-4 are above the plane of the pyranose chair and below at G3,whilst axial substituents at C-2 and C-4 are below the plane and above at C-3. The mean values for each of these types are in Table 1. TABLE 1.Proton chemical shifts (T values) exo-Axial 7*85t endo-Axial 7*88t exo-Equatorial 8.00 endo-Equatorial 7.93 t The value for the D-galacto-isomer is excluded since it showed coincident axial resonances (T 7-82). Further evidence for the validity of these assign-ments came from a study of the acetoxy-methyl resonances of the 3-acetarnido-2,4-di-O-acetyl-1,6-anhydro-3-deoxy-derivatives$ of D-altropyranose (VII) (T 7-91 and 7-84) D-idopyranose (IX) (T 7-91 and 7-91) and D-gulopyranose (VIII) (T 7-91 and 7.83). In the case of the isomers (I), (11) (IV) (VI) 07111 and (VlII) the multiplets due to all of the ring hydrogens were assigned and a detailed discussion of the conformational significance of the coupling constants obtained from these spectra will be given el sewhere.Spin-spin coupling constants in saturated systems are usually observed between hydrogen substituents separated by two or three bonds. Recently “long- * Kindly provided by Dr. N. K. Richtmyer. $ Kindly provided by Dr. A. C. Richardson. range” couplings have been observed2 in saturated systems where the hydrogen substituents are separated by four bonds but in all cases the coupling occurs only when the protons have some specific rela-tive orientation. In the 1,6-anhydro-derivatives GI) (III) and (VI) long-range couplings between H-1 and H-3 of 1.3 1-4 and 1.8 C.P.S. (first-order analysis) respectively were observed. In these com-pounds the hydrogen substituents are in 1,3-&equa-torial positions on the pyranose chair conformation and no coupling was observed in any of the other compounds where H-3 was axial.This is the first long-range coupling to be observed in a carbo-hydrate system and the precise stereochemistry necessary for such coupling is clearly defined. Compound 2-0Ac 3-OAc 4-OAc ax eq ax eq ax eq D-altro (I) 7.91 8-00 7-85 D-ghC0 (11) 7.84 7.89 7-86 D-manno (111) 7.94 7-86 7.84 D-gUl0 Ov) 7.86 8-01 7-94 D-id0 (V) 7.94 7.98 7-92 D-galacto (VI) 7.82 7.82 7.92 One of us (L.D.H.) thanks the Department of Scientific and Industrial Research for a maintenance allowance and the National Physical Laboratory for facilities as a guest worker (1962). (Received November Sth 1962.) Lemieux Kullnig Bernstein and Schneider J.Amer. Chem. Soc. 1958 80 6098. a Davis Lutz and Roberts,J. Amer. Chem. Soc. 1961 83 246; Meinwald and Lewis ibid. p. 2769; het Cmtad. J. Chem. 1961,39 789; Abraham and McLauchlan Mol. Phys. 1962,5 195. DECEMBER 1962 383 Total Synthesis of the Calycanthaceous Alkaloids. chimonourthine RICHARD By JAMESB. HENDIUCKSON Rms and RICHARDGOSCHKE (DEPARTMENT UNIVERSITY LosANGELES, OF CHEMISTRY OF CALIFORNIA U.S.A.) THE impetus for the correct formulation of the calycanthaceous alkaloids came from a considera- tion of their biogenesisl by oxidative dimerisation of N-methyltryptamine. Hydrolysis of the resultant in- dolenine dimer affords the dialdehyde (I)which may now undergo cyclisation to any of five structural isomers (11) labelled a-e.As these hydrolytic inter- conversions are all equilibria it was arguedl that the thermodynamically most stable isomer (a) was natural calycanthine a conclusion supported by nuclear magnetic resonance studies1 and X-ray crystallography.2 A natural isomer of calycanthine was later found in chimonanthine,3 shown to be the (-))y-isomer,4ss and two more alkaloids calycan- thidine and folicanthine are respectively mono- and di-N-methyl derivatives of this.6 We approached the total synthesis of these alkaloids by a similar route but a number of oxida- tive experiments on N-ethoxycarbonyltryptamine yielded only intractable material. 2,3-Dihydro-2- oxotryptamine (111; R = H) was prepared by an improved previous synthesiss and converted by ethyl chloroformate into the urethane (111; R = C02Et).Oxidative dimerisation of the sodium salt of the urethane with iodine in tetrahydrofuran followed by chromatography on alumina yielded the two diastereomeric dimers (IVa and b; R = CH,CH,.NH.CO,Et) m.p. 243-245" and 214-216". As the bis-oxindole (IV; R = H; obtained from isoindigo) had been converted1 by acid hydrolysis into the compound (V; R = H) contain-ing the calycanine skeleton the dimers (IVa and b) were subjected to a variety of solvolytic conditions in attempts to prepare the calycanthine precursor (v; R = CH,-CH,-NHCO,Et) but only the starting materials or the amines (IV; R = CH2CH2*NHd were obtained in contrast to the behaviour of the parent compound (V; R = H). Reduction of compound (IVa) by lithium alumin- ium hydride in refluxing tetrahydrofuran yielded an isomer m.p.240-243" of calycanthine believed to be the meso-E-isorner because of two N-CH peaks in the nuclear magnetic resonance spectrum and a decrease in the ultraviolet maximum at 278 mp to half its intensity in acid (this peak is essentially destroyed by acid in indolines but retained intact in calycanthine and other Ar.N-CH-N systems). Similar reduction of the isomer (In)afforded the y-isomer (chimonanthine) m.p. 202-203 " identical with nat-ma1 (-)-chimonanthine* in its infrared spectrum in chloroform and its mass spectrum? as well as in thin-layer chromatographic mobilities in several sol- vents; these properties were markedly different for * Kindly supplied by Dr.G. Smith Manchester whom we thank warmly. t Mass spectra were kindly determined by Professor K. Biemann M.I.T.; they show two major peaks at and 172 which are rationalised by the y-structure. Woodward Yang Katz Clark Harley-Mason Ingleby and Sheppard Proc. Chem. Soc. 1960,76. Hamor Robertson Shrivastava and Silverton Proc. Chem. Soc. 1960,78. Hodson Robinson and Smith Proc. Chem. SOC.,1961,465. Grant Hamor Robertson and Sim Proc. Chem. Soc. 1962,148. Saxton Bardsley and Smith Proc. Chem. SOC.,1962 148. 'Cf. Harley-Mason and Ingleby J. 1958 3639. PROCEEDINGS the other isomers, but do not definitely preclude the maximum on acidification (cf. the ecompound meso-isomer; resolution studies to clarify this are in above).It seems probable that all five of the optically progress. active isomers of calycanthine will be found in Studies in hydrolytic conversions of the above into Nature. the other calycan&ne isomers are in progress pre- liminary results indicating the formation of caly- The authors acknowledge their indebtedness to the canthine (a)as well as others from the y-structure National Science Foundation for support of this while in the other diastereomeric series the isomer work to Dr. F. J. Petracek of Riker Laboratories for (E) from (IVa) yields in aqueous acid a third caly- many valuable discussions to Professor R. B. canthine isomer m.p. 204-205” (different from the Woodward of Harvard University for gifts of y-isomer above) the structure of which has not yet (-)-calycanthine and the compound (V; R = H) been assigned.The alkaloid hodgkinsine7 is also an and to the Alfred P. Sloan Foundation for a fellow-optically active isomer of calycanthine which is ship (to J.B.H.). probably the &isomer as it yields no calycanine on Added in proofi Both meso-and (-+)-chimonanthine degradation (expected from the p-structure) and have since been obtained crystalline. shows no diminution of intensity in the ultraviolet (Received October 25th 1962.) 7 Anet Hughes,and Ritchie Austral. J. Chem. 1961 14 173. $ The spectra and analyses of all compounds described herein are consistent with their formulations and will reported in greater detail at a later date. The Oxidation of RS-Ions by Electron-accepting Species By THOMAS HARVEY ~OBNER,and ALANSCHRIEsHErM J.WALLACE JAMESM. MILLER @SO RESEARCH AND ENGINEERING COMPANY PROCESS RESEARCH DIVISION, ANALYTICAL LINDEN,N.J. U.S.A.) RESEARCHDIVISION WErecently observed that dipolar solvents such as fold with dimethylformamide). The nitrogen coupling dimethylformamide and dimethylacetamide had a constant for the nitrobenzene radical-anion under marked effect on the rate of oxidation of RS-ions by these conditions was 10.1 f0.1 gauss in agreement molecular oxygen? We have since examined the with the value of 10.3 gauss reported by various oxidation of various such ions by electron-accepting workers2 for other solvent systems. A slow decrease species in dmethylf’ormamide. in resolution due to the hydrogen splitting was In a typical experiment butane-1-thiol (0.025 observed but the basic six-line spectrum due to the mole) was added to a 1.33hl-degassed “solution” nitrogen splitting did not change.(37.5 ml.) of potassium hydroxide in dimethyl- The dour change was also studied spectrophoto- formamide* in a nitrogen dry-box at 25”. Nitro-metrically. The visible absorption maximum was at benzene (0.025 mole) was then added the flask was 457 mp; the increase in its intensity for the first sealed and the mixture was stirred for 3 hours. After 100 min. followed first-order kinetics. On exposure 1 min. a yellow colour developed changing in 2-3 to oxygen the absorption maximum disappeared min. to red and then gradually transformed to dark indicating that the anion-radical was destroyed. This blue.After neutralisation gas-chromatography is typical of stable radical species and is further established that the oxidation product was n-butyl evidence for the radical-anion? In an examination of disulphide and analysis indicated 99 % conversion of the scope of this reaction it was found that toluene- the thiol and a 98% yield of disulphide which were a-thiol and thiophenol were converted into their di- confirmed by the gas-chromatographic data. sulphides in yields of 81% and 2 % respectively. This These results suggested that the oxidation was due reactivity sequence suggests that the rate-determining to reduction of the nitrobenzene to its radical-anion step is transfer of an electron from the RS-ion to O2N-C,H,.-,t and this was confirmed by electron- nitrobenzene.A similar reactivity sequence has been spin resonance and ultraviolet and visible absorbance observed in the oxidation of numerous such ions by measurements (for these measurements 1 ml. por-oxygen.* tions of the above reaction mixture were diluted ten- The reaction also appears to be fairly general as * t Similar observations The potassium hydroxide was not completely dissolved. havc recently been observed by G. A. Russell and E. A. Janzen in the reaction of carbanions with nitrobenzene (Preprints Petr. Div. of her. Chem. SOC. 7 C-81 Sept. 9-14 1962. l Wallace and Schriesheim J. Org. Chem. 1962 27 1514. Geske and Maki J. Amer. Chem. SOC.,1960 82 2671 ;Ward ibid. 1961 83 1296; Piette Ludwig and Adam Analvt. Chem. 1962 34 916. 3 Walling “Free Radicals in Solution,” John Wiley and Sons New York 1957 Chapt.10. 4 Wallace Schriesheim and Bartok J. Org. Chem. to be published. DECEMBER 1962 far as the oxidising agent is concerned. For example 2-nitrothiophen tetracyanoethylene and 4-nitro-pyridine N-oxide also promoted it. CNitropyridine N-oxide which is the most electronegative species studied was the most active oxidising agent since it 385 oxidised PhS- and BUS- to their disulphides at the same rate. meauthors are indebted to Dr. George ~hfor his aid in interpreting the electron-spin resonance results. (Received October 11th 1962.) The Stereochemistry of Glauconic Acid By G. FERGUSON ROBERTSON G. A. SIM,and J. MONTEATH DEPARTMENT GLASGOW CRYSTALLOGRAPHY (CHEMISTRY THEUNIVERSITY W.2 and CHEMICAL LABORATORY THE UNIVERSITY OXFORD) WErecently reported1 that an X-ray crystal analysis of byssochlamic acid bis-p-bromophenylhydrazide had established the constitution and relative stereo- chemistry shown in (I) for byssochlamic acid the characteristic metabolite of Byssochlamys fulva.Barton Sutherland and their collaborators simul- taneously reported3 degradative and spectroscopic studies of byssochlamic acid and of glaucanic and glauconic acids metabolites of Penicillium purpuro- genum ;glaucanic acid was assigned formula (I1;R = H) and glauconic acid formula (11; R = OH) and the constitution (I) was independently suggested for byssochlamic acid. Some aspects of the stereochemistry of glauconic acid clearly merited further attention and at the sug- gestion of Professor D.H. R. Barton F.R.S. we undertook an X-ray analysis of glauconic acid rn-iodobenzoate. We find that this derivative has the constitution and relative stereochemistry given in (111; R = rn-BrC,H,CO,); it follows that the stereochemistry of glauconic acid is actually as in (111; R = OH) with the oxygen substituent at posi- tion 4 in the opposite configuration to that proposed earlier.3 Glauconic acid rn-iodobenzoate crystallises in the orthorhombic system space group P22,2, with four molecules of C25H,310,in the unit cell of dimensions a = 8.02 b = 13.65 c = 2250 A. From equi-inclination Weissenberg photographs 1700 inde-pendent structure amplitudes were evaluated. The crystal structure was elucidated by three-dimensional Fourier methods.The value of R is now 19.6 % and refinement of the atomic co-ordinates is continuing. The conformation of the nine-membered ring is demonstrated in the Figure. X 7 The atomic arrangement in a molecule of glauconic acid m-iodobenzoate as viewed along the c-axis of the crystal. For the calculations on the Glasgow University DEUCE computer programmes5 devised by Dr. J. S. Rollett and Dr. J. G. Sime were employed. (Received November 6th 1962.) Hamor Paul Robertson and Sim Experientia 1962 18 352. Raistrick and Smith Biochem. J. 1933,27 1814. Baldwin Barton Bloomer Jackman Rodriguez-Hahn and Sutherland Experientia 1962 18 345, * Wijkman Annalen 1931 485 61. “Computing Methods and the Phase Problem in X-ray Crystal Analysis,” ed.Pepinsky Robertson and Speakman Pergamon Press Oxford 1961; Rollett p. 87; Sime p. 301. PROCEEDINGS Sensitised Anti-Stokes Delayed F'luorescence By C. A. PARKER and C. G. HATCHARD (ROYALNAVAL ADMlRALTy MATERIALS Smmc SERVICE LABORATORY HOLTON DORSET) HEATH,POOLE WEhave previously observed delayed fluorescence from solutions of anthracene? phenanthrene,l pyrene,2 and na~hthalene.~ The intensity was pro- portional to the square of the rate of absorption of exciting light. With anthracene phenanthrene and naphthalene at room temperature the spectra were almost identical with those of normal monomer fluorescence; but with pyrene at room temperature and with naphthalene at -105" delayed emission was observed both from the excited monomer and from the excited dimer.The results were interpreted by a mechanism in which triplet-triplet quenching pro- duces a system of excited dimers one of which emits and/or dissociates into excited and unexcited singlet monomer. The phenanthrene-sensitised delayed fluorescence. of anthracenel was also tentatively interpreted by a similar mechanism in which the first stage involves triplet energy transfer from phen- anthrene to anthracene. The proposed mechanism requires that part of the Wavelength (mp) energy from two separately absorbed quanta be FIG. 1. (1 2) Delayed fluorescence from lo-%-transferred to the same molecule. Thus by choosing phenanthrene and from mixture of phenanthrene as sensitiser (donor) a compound whose lowest (lo-%) and naphthalene (3 x lo-%) in ethanol.excited singlet state lies below that of the acceptor (3) Normalfluorescence from solutions (1) and (2) at but whose triplet state lies above that of the acceptor 260 times less sensitivity. (4) Spectral distribution of it should be possible to cause the acceptor to emit exciting light for curves (l) (2) and (3). -0-7x 1O-g delayed fluorescence having a frequency higher than einstein l.-l sec.-l absorbed. (5,6) Normal and delayed that of the exciting light. To test this prediction two fluorescence from 3 x 10%-naphthalene in ethanol systems were chosen namely (1) phenanthrene excited by 313 mp. -2 x einstein l.-l sec.-l (donor) naphthalene (acceptor) and (2) proflavine absorbed.Curve (5) at a sensitivity 100 times less than hydrochloride (donor) anthracene (acceptor). curve (6).Temperaturefor all curves was -72" f3OC. For the first system exciting light of wavelength 341-362 mp isolated from the light of a mercury- 436 mp,isolated from the light of a mercury lamp by cadmium lamp by filters was used. Its spectral dis- means of a monochromator and yellow filter was tribution is shown in Fig. 1 (curve 4). The short- used. This light was absorbed by the proflavine wavelength components of the filtered light were hydrochloride but not by the anthracene. The spec- absorbed quite strongly by 10-3~-phenanthrene but trum of normal fluorescence thus showed only the not at all by 3 x 10-%-naphthalene (as judged by band due to the proflavine hydrochloride but the the absence of fluorescence and delayed fluorescence spectrum of delayed fluorescence showed mainly from a solution containing only naphthalene).With the bands due to anthracene (Fig. 2) at a quantum a solution containing both phenanthrene and efficiency of about 0.1 %. naphthalene quite intense bands of naphthalene de- In both systems the most energetic quanta emitted layed fluorescence were emitted (quantum efficiency carried considerably greater amounts of energy than 7 1%; see Fig. 1 curve 2). These were readily those of the exciting light. The excess was more than identified by comparison with the spectra obtained 5 kcal. mole-l for the first system and 9 kcal.mole-l when a solution of naphthalene alone was excited by for the second.(Had the proflavine hydrochloride light of shorter wavelength (Fig. 1 curves 5 and 6). been excited at the wavelength of its absorption For the second system exciting light of wavelength maximum the excess would have been over 12 kcal. Parker and Hatchard Proc. Chem. SOC.,1962 147; Parker and Hatchard Proc. Roy. SOC.,1962 A 269 574. Parker and Hatchard Trans. Faraday SOC. 1963,59 in the press. Parker unpublished work. DECEMBER 1962 387 mole-l.) The results thus provide convincing evidence that a two-quantum process is involved. Further since the first system is one in which triplet energy transfer is known to occur it seems likely that it is the triplet which participates in the produc- x 4 .-tion of delayed fluorescence.We therefore propose u) the following mechanism in which N2*and N2** C .+ are excited naphthalene dimers similar to those pro- c -posed for pyrene :2 hv 400 440 480 520 P -f P* -+ 3P Wavelength (my) *P + N -+ P + 3N FIG. 2. Normal fluorescence (curve 1) and delayed 3N + sN4N,* + N,** + N* + N fluorescence (curve 2) from a solution containing N*+N + hv' lW%-proflavine hydrochloride and 5 x 10"'~-anthracene in ethanol excited by 436 mp. -3 x 10-6 The mechanism proposed for the second system is einstein I.-l sec.-l absorbed. Curve (1) at a sensitivity analogous although the overall process seems to be 3000 times less than curve (2). Temperature was less efficient. -66" 3"~. (Received October 25th 1962.) ' Porter and Wilkinson Proc.Roy. Soc. 1961 A 264 1. A Comparison of the Bond Lengths in (NSF), (NSCI), and a-(NSOCl) By G. A. WIEGERS Vos and AAFJE (LABORATORIUM RIJKSUNIVERSITEIT, VOOR STRUCTUURCHEMIE GRONINGEN THENETHERLANDS) COMPOUNDS with six- or eight-membered rings of the three compounds are listed in Table 1. The centro- alternating sulphur and nitrogen atoms have recently symmetric space groups Pnma and P2,/m7 respec-aroused considerable interest in connexion with the tively were adopted during the refinement of bonding properties of their n-electrons. To study the a-(NSOCl)3 and (NSCI),. About 180 independent influence of substituents on the bond lengths and reflexions were available for (NSF), 500 for angles in the ring the crystal structures of (NSF) a-(NSOCl), and lo00 for (NSCl),.The final values at 20" a-(NSOCl) at 20° and (NSCl) at -130" for the residuals are 5.6% 4.7 % and 6-9% respec-were determined and refined with three-dimensional tively for the observed reflexions. Anisotropic TABLE1. Cell dimensions (A) possible space groups and number of molecules in the unit cell. (NSF) CX-(NSOCI) (NSC03 a = 9.193 f0-005 a = 7.552 f0.002 a = 5.49 f0.03 b = 11.540 & 0.002 b = 11-14 f005 c = 4.299 5 0.003 c = 10.078 f0.003 c = 6.05 & 0.03 18 = 98.4 & 0-4 Pa 2,c Pnma or Pn2,a P2,frn or P2 z=2 z=4 2=2 data. The results of our two-dimensional refinement thermal motion was considered for a-(NSOCl) but of (NSF) have already been published." Recently it for (NSCl) and (NSF) only isotropic temperature appeared from a Communication in these Proceed-factors were taken into account.ings that the structure of a-(NSOCl) has also been The structure of (NSCl) is shown in the Figure. determined by Bannister and Hazell. Their bond Both this and a-(NSOCl) have a chair form the lengths and angles agree well with our values quoted nitrogen atoms on the average being 0.18 and 0.25 A below. respectively from the plane through the sulphur The cell dimensions and possible space groups of atoms. All chlorine atoms are in axial positions. C+g J. 1959 997; Dewar Lucken and Whitehead J. 1960,2423. a Wiegers and Vos,Acta Crysf.,1961 14 562. Bannister and Hazell Proc. Chem. SOC.,1962,282. PROCEEDINGS TABLE 2. Bond lengths (A) and bond angles.(NSF),Value E.s.d. a-(NSOCI),Value E.s.d. (NSCO,Value E.s.d. N-S 1.660 1.540 0.01 1.564 0.008 1.605 0.01 %Hal 1.602 0.006 1-995 0.004 2-150 2*084* 0-01 SO 1.403 0.008 N-S-N 111.7" 0.6" 113.0" 0.5" 113.4" 0.5O S-N-S 123.9 0.6 122.0 0-5 123-8 0-5 N-S-0 111.8 0-5 N-S-Hal 91-5 106-2 0-4 106-4 0.4 113.8 0-5 0-%Hal 107-0 0-4 * This difference in bond lengths may be due to different environments of the chlorine atoms. The Figure in our previous paper2 shows the struc- ture of (NSF),. The bond lengths and angles are given in Table 2; onIy average values are listed for crystallographically non-equivalent bond lengths and angles which agree within experimental error. The N-S bond lengths in the eight-membered ring of (NSF) are alternatingly different.For (NSCl) and a-(NSOCl) refinement in the centrosymmetric space groups yielded equal lengths for the N-S bonds. Equally good agreement can however be obtained between observed and calculated structure factors for unequal lengths of these bonds if the space groups are assumed to be non-centrosymmetric. (Received October 4th 1962.) The Structure of ( -)-Trisoxalatocobalt(m) By A. J. MCCAFFJBY and S. F. MASON (CHEMISTRY THEUNIVERSJTY DEPARTMENT OFEXETER) A RECENT proton magnetic resonance study1 of potassium trisoxaIatorhodium(m) shows that the solid with either 4.5 or 1.0 molecule of water of crystallisation consists of an equimolecular mixture of the dihedral (0,) complex ion [I; M = Rh(111)l and the ion with approximate C symmetry [II; M = Rh(m)].The monohydrate is isomorphous2 with the corresponding cobalt(m) salt and the present circular dichroism measurements (Figure) indicate that in solution the (-)-trisoxalatocobalt(m) ion exists partly in the form [II; M = CO(III)]. The lower-energy Tl and the higher-energy T2 electronic transitions of octahedral strong-field ds metal ions break down in the corresponding 0,com-plexes e.g. (I) into A + Ea components and into Al + Eb components respectively. The transitions with A2 Ea and Eb symmetry in D are formally allowed in both magnetic and electric dipole radia- tion fields and they should have finite rotational strengths whereas the A transition is forbidden having zero rotational strength. In the corresponding C complexes to which (11)approximates the Tl and T2transitions of the octahedral ion each break down into one A and two B components all of which are allowed with finite rotational strengths.Thus a dis-symmetricds (or d3)complex with C symmetry may give two or three circular-dichroism bands in the wavelength region of the higher-energy ligand-field absorption band whereas the corresponding D complex can give no more than one circular-dichroism absorption in that region. Authentic 0 complexes conform to this expectation,3s4 and the observation (Figure) that in solution the (-)-tris- oxalatocobalt(1n) ion gives two circular-dichroism bands in the 4oo(r-5000 A region indicates that some of the ions have an approximate C symmetry prob- Porte Gutowsky and Harris J.Chem. Phys. 1961,34 66. Jaeger Rec. Trav. chim. 1919 38 113. Mathieu J. Chim. phys. 1936,33 78. Ballard McCaffery and Mason Proc. Chem. Soc. 1962,331. DECEMBER 1962 ably [II; M = Co(m)]. The trans-isomer of (11)is not dissymmetric and would give no circular-dichrosim absorption. Mathieu5 observed that 0,metal complexes give circular-dichroism bands more intense by a factor of 4-9 than those of the corresponding C,complexes with two monodentate ligands. The circular-dichro- ism absorptions of the (-)-trisoxalatocobalt(ru) ion and of authentic D ~omplexes~~~ have similar magni- tudes suggesting that in solution the (-))-trisoxalato- cobalt(m) ion exists partly in the D form D; M = Co(m)] the fractional proportion probably being comparable to that of [II; M = Co(n1)1.In the colourless diluent crystal NaMgAl(C,0,),,9H20 which belongs to the hexa- gonal system the (-))-trisoxalatocobalt(m) ion gives for radiation propagated along the optic axis of the crystal only circular-dichroism bands with a positive sign (Figure). This mode of propagation can give rise only to transitions of E symmetry in the D3 complex so that the Ea transition has a positive rota- tional strength indicating4 that the 0 form of the (-)-trisoxalatocobalt(m) ion has the absolute con- figuration [I;M = CO(III)]. Since the C,form of the ion is probably derived from the D3 form without inversion the former has the absolute configuration [n; M = Co(m)] or the analogous structure in which the positions of the hydroxyl and the mono- dentate oxalate group are interchanged.n -I 4 4000 60 Wavelength (r The circular dichroism (. -.) and the electronic absorp- tion spectrum (-) of the (-)-trisoxalatocobalt(m) ion in solution and the circular dichroism (--) of the ion in the diluent crystal NaMgAl(C,04),,9H,0 with radiation propagated along the optic axis. The authors are indebted to the Wellcome Trustees for the provision of a spectropolarimeter and to the Royal Society Messrs. Albright and Wilson Ltd. and the Imperial Chemical Industries Limited for the components used in the construction of the circular-dichroism spectrophotometer. (Received November lst 1962.) Mathieu “Contribution to the Study of Molecular Structure,” Commemorative Volume to Victor Henri Desoer Liege 1947 p.11 1. Piper and Carlin J. Chem. Phys. 1961,35 1809. A Simple Preparation of Xenon Tetrafluoride By J. H. HOLLOWAY and R. D. PEACOCK (CHEMISTRY UNIVERSITY BIRMINGHAM, DEPARTMENT OF BIRMINGHAM 15) CONSIDERABLE interest has been aroused by the recent synthesis of xenon tetrafluoride from the elements in a static system at 400O.l We have confirmed that xenon and fluorine combine to form a compound of this composition and find that a simple flow method gives a yield of 30-50 %. Xenon gas (500 ml.) was allowed to diffuse into a stream of hydrogen fluoride-free fluorine (6 l./hr.) over a period of about 24 hours. The,central portion Claassen Selig and Malm J.Arner. Chem. Soc. 1962 of a 4 ft. length of nickel tube (4 in. outside diameter) packed with nickel sheet (R in Figure) which served as a reaction vessel was maintained at dull red heat by means of three Bunsen burners. The tetrafluoride which is appreciably volatile at 20° was collected in trap A which was cooled in acetone-solid carbon dioxide and the unchanged xenon was held in traps B and C cooled in Iiquid oxygen. Xenon tetrafluoride forms white crystals which 84,3593. PROCEEDINGS volatilise without decomposition in a nitrogen ion are formed quantitatively according to the equa- stream under heat supplied by a hair dryer (100- tion XeF 3-41-+ Xe + 21 + 4F-. This reaction 140”). We find like the American workers that was utilised by us in determining the composition of f2-c R r E - i A B C -72’ -180’ -180’ the compound does not attack glass at 20° and the compound Found Xe (by displacement) 63.5; it has been stored for several weeks at -25” F (as PbClF) 36.6; F (as iodide equiv.) 33.4.without change. Xenon tetrafluoride dissolves quietly XeF requires Xe 63.3; F 36-7%]. in potassium iodide solution and xenon and fluoride (Received October 30th 1962.) The Kinetics and Mechanism of the Reaction of Hexachlorocyclotriphosphazatriene with Piperidhe in Toluene By B. CAPON and R. A. SHAW K. HILLS OF CHEMISTRY COLLEGE OF LONDON, (DEPARTMENT BIRKBECK UNIVERSITY MALETSTREET W.C. 1) LONDON INspite of current interest in the chemistry of the catalysis in the displacement reactions of halogeno-chlorophosphazenesl and in their reactions with nitrobenzene derivatives indicates incursion of a amines2no kinetic studies have been described except tetraco-ordinate intermediate and our results for We now report hexachlor oc yclo t rip hosphaza t r iene may be inter-for one preliminary comm~nication.~ a kinetic investigation of the reaction of hexachloro- preted similarly in terms of a pentaco-ordinate inter- cyclotriphosphazatriene N3P3Cl (8-5 x lOV3~) mediate although the possibility of a one-step with piperidine (8.6 x 1.29 x lo” and 1.72 termolecular reaction is not completely excluded.x ~O-,M) in toluene at 0-O”,conditions which afford Preliminary results indicate that pentachloro-an 85 % yield of pentachloropiperidinocyclotriphos-piperidinocyclotriphosphazatriene reacts about 50 phazatriene N3P3Cl,(NC,H o).The reaction shows times and 2,2,4,6-tetrachloro-4,6-dipiperidinocyclo-mixed second- and third-order kinetics (k,= 2.2 x triphosphazatriene N3P,C14(NC,H,,), 500 times 1. mole-l sec.-l k3 = 1.7 1.2 sec.-l) and more slowly with piperidine whilst octachlorocyclo- is catalysed by tri-n-butylamine (k’3 = 1.4 x tetraphosphazatetraene N4P4Cl, reacts 1 02-lo3 1. mole- sec.-l). This behaviour is similar to times faster than hexachlorocyclo trip hosphaza triene that observed for the reaction of l-chloro-2,4-di- with diethylamine. nitrobenzene with aliphatic amines in chloroform,1 but the third-order term in the present study is rela- One of us (K.H.) thanks D.S.I.R.for a main-tively more important than those observed in the tenance grant. benzenoid system. It is now accepted4 that base- (Received November 2nd 1962.j 1 Shaw Chem. and Ind. 1959,412; Paddock and Searle in Emelkus and Sharpe’s “Advances in Inorganic and Radio-chemistry,” Academic Press Inc. New York 1959 Vol. I p. 348; Gribova and Ban-yuan Russ. Chern. Rev. 1961 1,l; Shaw Fitzsimmons and Smith Chem. Rev. 1962,62,247. * Becke-Goehring and John Angew. Chem. 1958 70 657; Becke-Goehring John and Fluck 2.anorg. Cheni. 1959,302,103; Ray and Shaw,Chem. and Ind. 1959,53; J. 1961,872. 8 Bailey and Parker Chem. and Ind. 1962 1823. 4 Ross and Finkelstein J. Amer. Chem. Soc. 1957 79 6547; Ross and Petersen ibid. 1958 80 2447; Bunnett, Quart. Rev. 1958 12.1; Bunnett and Randall J. Amer. Chem. SOC.,1958 80 6020; Ridd Ann. Reports 1960 57 189; Hine Ann. Rev. Phys. Chem. 1960 11 75; Chapman Chaudhury and Shorter J. 1962 1975. ERRATUM IN the communication by Arden and Phillips (Proceedings 1962 354) line 11 from the bottom of the right-hand column should have been placed at the top of that column. In eqn. (10) on p. 355 for H read N,. DECEMBER 1962 391 NEWS AND ANNOUNCEMENTS Vacancies on Council 1963.-Notice is hereby given that in accordance with the Bye-Laws the following vacant places in the Council fall due to be filled at the Annual General Meeting to be held in Cardiff on Thursday March 28th 1963. No. of Names of Members who are Oflce vacancies to retire Vice-Presidents who have not filled the Office of President.. .. TWO Professor E. R. H. Jones Professor M. Stacey Elected Ordinary Members of Council Constituency I .. .. .. (South-East England-Northamptonsh$e .. .. (including the .. Soke .. of TWO Dr. E. A. Moelwyn-Hughes Dr. L. Crombie Peterborough) Huntingdonshire Cambndgeshire (mcluding the Isle of Ely) Norfolk Suffolk Essex Middlesex London Hertfordshire Bedfordshire Buckinghamshire Oxfordshire Berkshire Hampshire (including the Isle of Wight) Surrey Sussex Kent and the Channel Islands.) Constituency I1 .. .. *. .. .. .. .. ONE Professor J. C. Robb (Central and South-West England and South Wales-Staffordshire Shropshire Herefordshire Worcestershire Warwickshire Gloucester- shire Wiltshire Dorsetshire Somerset Devonshire Cornwall Mon- mouthshire Cardiganshire Radnorshire Pembrokeshire Carmarthen- shire Brecknockshire and Glamorganshire.) Constituency I11 .. .. .. .. .. .. .. ONE Professor R. N. Haszeldine (North-West England North Wales and Isle of Man-Cumberland, Westmorland Lancashire Cheshire Flintshire Denbighshire Mont- gomeryshire Merionethshire Caernarvonshire Anglesey and the Tsle of Man.) Constituency V . . .. .. .. .. .. .. ONE Professor R. A. Raphael (Scotland.) With the exception of Dr. L. Crornbie who was appointed under Bye-Law 42 the members who are to retire are not eligible for reelection to the same office until a lapse of one year. No vacancy arises in Constituencies IV or VI. Nominations by Fellows for the Office of Vice-President who has not filled the Oflice of President should be made in writing and must be signed by at least twenty Fellows.Fellows resident in a constituency may nominate any Fellow in that constituency for election to the Council to fill a vacancy among Elected Ordinary Members of Council allotted to that constituency. Every such nomination must be in writing signed by at least fifteen Fellows resident in that constituency. Fellows may obtain forms of nomination from the General Secretary and should state the vacancy for which they are requested. Every nomination must relate to one vacant place only and must be accompanied by a signed declaration by the nominee that he is willing to accept office if elected. Nominations must be received by the Society not later than Thursday February 14th 1963.A. W. JOHNSON K. W. SYKES J. W. LINNETT Honorary Secretaries. Local Representatives for St. Andrews and agreed to act as Chemical Society Liaison Officers Dundee.-Dr. C. Horrex has been appointed to act British Titan Products as Local Representative at St. Andrews. Dr. D.E. Billingham .. .. Dr. A. E. Comyns Hoare who has hitherto been responsible for the University of Sussex whole area will continue as Local Representative at Brighton .. .. .. Dr. R. A. Jackson Dundee. Shirley Institute Manchester Dr. F. S. H. Head Liaison Officers.-The following Fellows have Nobel Prize -The Nobel Prize for Chemistry for 1962 has been awarded jointly to Dr. J. C. Kendrew and Dr. M. F. Perutz for their studies of the struc- tures of globular proteins.Royal Society Medals.-Medals have been awarded to the following The Copley Medal to Sir CyriZ Hinshelwood for his distinguished researches in the field of chemical kinetics including the study of biological reaction mechanisms and for his outstanding contributions to natural philosophy. The Rumford Medal to Professor D. M. Newitt for his distinguished contributions to chemical engineering. The Davy Medal to Professor H. J. Enzelius for his distinguished researches in inorganic chemistry and the discovery and examination of a wide range of new compounds. Election of New Fellows.-48 Candidates whose names were published in the Proceedings for October have been elected to the Fellowship. Death.-The death on November 18th 1962 of Professor Dr.Niels Bohr is announced with regret. Professor Bohr was elected an Honorary Fellow of the Society in 1929. We also regret to announce the deaths of the following Fellows Captain A. Bracher (21.5.62) of Bradford-on-Avon formerly Director United Dairies Limited; Dr. B. G. Engel (17.9.62) of Monsanto Research S.A. Zurich; Dr. L. E. Hinkel (18.11.62) of Swansea formerly Senior Lecturer in Organic Chemistry at University College Swansea; Dr. E. J. King (31.10.62) Professor of Chemical Pathology at the Postgraduate Medical School London W.12; Mr. A. G. Lidstone (30.10.62) of London N.W.3; Professor B. C.McEwen (9.1 1.62) of Hove formerly Science Professor The Nizam’s College Hyderabad; Dr. H. A. E.Mackenzie (April 1962) Deputy Manager African Explosives and Chemicals Limited Johannesburg; and Mr. E. H. Miller (2.2.62) of Victoria Australia a Fellow for more than 60 years. University of Sussex.-The teaching of Physical Sciences has begun with 160 first-year under-graduates of whom 80 take Chemistry. About 60 of these will probably go on to graduate in Chemistry. In addition six full-time research students are starting work for Sussex higher degrees during this present session and two post-doctoral Fellows will join the laboratory early in 1963; subsequently a rapid build-up of research is planned. Academic posts for the 1963-64 session are currently being advertised. Details of the Chemistry staff are as follows Professor C.Eaborn formerly Reader in the University of Leicester. PROCEEDINGS Senior Lecturer Dr. E. R. A. Peeling formerly Senior Lecturer in the University of Leicester. Lecturers Dr. C. N. Banwell formerly Research Fellow of Magdalene College Cambridge. Dr. E. 0.Bishop formerly Research Fellow in the University of Oxford. Dr. R. A. Jackson formerly I.C.1. Fellow in the University of Leicester. Dr. J. D. Smith formerly Lecturer in the University of Leicester. Mr. A. Pidcock formerly of the University of Oxford. Annual Exhibition of the Institute of Physics and The Physical Society.-The Exhibition of Scientific Instruments and Apparatus for 1963 will be held at the Royal Horticultural Society’s Old and New Halls London S.W.l on Monday January 14th to Thursday January 17th.Fellows of The Chemical Society may obtain tickets to visit the Exhibition during the closed session on Tuesday morning January 15th when the Exhibition is not so crowded. Applications for tickets should be made to the General Secretary The Chemical Society Burlington House London W.l. Symposia etc.-A Symposium on Recent Develop- ments in the Chemistry of Genetic Processes will be held at the Bradford Institute of Technology on February 9th 1963. Further enquiries should be addressed to Dr. R. P. Sheldon Department of Chemical Technology Bradford Institute of Tech- nology Great Horton Road Bradford 7. The First European Symposium on the Cleaning of Coke Oven Gas sponsored jointly by the European Federation of Chemical Engineering Society of German Chemists and other organisa- tions will be held in Saarbriicken Germany on March 21st-22nd 1963.Further enquiries should be addressed to the Secretariat DECHEMA 25 Rheingau-Allee Frankfurt am Main Germany. The First International Meeting on Questioned Documents will be held at the School of Pharmacy London on April 17-1 8th 1963. Further enquiries should be addressed to the Secretariat 28 Portland Place London W. 1. N. Miller Memorial Meeting on Radiation Chem- istry will be held in Rocamadour (Dordogne) France from April 22nd-26th 1963. Further en- quiries should be addressed to Professor M. Magat Laboratoire de Chimie Physique Facult6 de Sciences Orsay (S.-et-O.) France.A Conference on Electronic Processes in Di- electric Liquids will be held in London on April 23rd-25th 1963. Further enquiries should be addressed to the Administration Assistant Institute DECEMBER of Physics and The Physical Society 47 Belgrave Square London S.W. 1. A Conference on Recent Advances in Polymer Science and Technology sponsored by the Plastics Institute the Society of Chemical Industry and the Institution of the Rubber Industry will be held in London from May lst-2nd 1963. Further enquiries should be addressed to the Secretary Plastics Institute 6 Mandeville Place London W. 1. The Fifth International Conference on Coal Science will be held in Cheltenham on May 28-3Oth 1963. Further enquiries should be addressed to R.G. J. Kingsmill Secretary General of the Conference National Coal Board Coal Research Establishment Stoke Orchard Near Cheltenham Gloucester. The Third Congress of the European Federation of Corrosion will be held in Brussels from June 4-7th 1963. Further enquiries should be addressed to Georges Biva Directeur SociCtC de Chimie Tndustrielle rue Joseph-I1,32 Brussels 4 Belgium. The Sixth International Symposium on Free RadicaIs sponsored by the Society of Chemical Industry will be held in Cambridge from July 2nd-Sth 1963. Further enquiries should be ad- dressed to Dr. A. B. Callear Secretary of the Symposium Department of Physical Chemistry Lensfield Road Cambridge. An International Conference of Nuclear Struc- tures will be held in Stanford California from July 8-1 lth 1963.Further enquiries should be addressed to Professor R. Hofstadter Department of Physics Stanford University Stanford California U.S.A. The Fifteenth International Symposium on Crop Protection will be held at Ghent on May 7th 1963. Further enquiries should be addressed to Prof. Ing. J. van den Brande Institut Agronomique de I’Etat Coupure Links 233 Ghent Belgium. The Fifth International Pesticides Congress will be held in London from July 17th-23rd 1963. Further enquiries should be addressed to the Secretariat Biochemcal Society 20 Park Crescent London W. 1. The Third International Symposium of Chemo- therapy will be held in Stuttgart from July 23rd- 27th 1963. Further enquiries should be addressed to Dr.H. P. Kuemmerle General Secretary The Inter- national Society of Chemotherapy Postfach 3030 Stuttgart 1 Germany. The Eighth Congress of the International Union of Leather Chemists’ Societies will be held in The Hague from August 26th-31st 1963. Further en- quiries should be addressed to P. E. van Kats Congresbureau van de Gemeente The Hague, Net herlands. The Fourth International Congress of Surface Activity organised by the European National Com- mittee of the ‘‘Cornit6 International de la De- tergence” will be held in Brussels on September 7-12th 1964. Further enquiries should be addressed to the Secretariat of the Congress 49 Square Marie- Louise Brussels Belgium. Personal.-Professor G. V. Bakore formerly of the Government College Ajnier is now Head of the Department of Chemistry at the newly established University of Jodhpur India.Mr. E. C. Brick is now Senior Lecturer in Organic Chemistry at the Central College of Further Educa- tion Eastham Wirral Cheshire. Dr. J. Chart of Imperial Chemical Industries Limited Heavy Organic Chemicals Division has been appointed Visiting Professor of Chemistry at Yale University for the Spring Semester of 1963. Dr. J. W. Cook has been appointed Chairman of the Government’s Advisory Committee on Poisonous Substances used in Agriculture and Food Storage. Dr. S. Cotson is the Head of the new Department of Chemistry and Chemical Technology formerly with the new Division of Food Science and Tech- nology part of the Department of Chemistry and Food Technology of Borough Polytechnic London S.E.l.Dr. W.C. Davey has retired as Chemical Research Manager at Dunlop Limited. Dr. G. P.Ellis formerly with Benger Laboratories Limited has taken up an appointment as Senior Lecturer in Organic Chemistry at the Welsh College of Advanced Technology Cardiff. Mr. B. A. FOX has been appointed Head of Department of Science and Food Technology at the Salford Technical College. Dr. H. D. Kay has retired as Director of Twyford Laboratories Limited and Dr. F. A. Robinson Chair-man of Crookes Laboratories Limited has been appointed Managing Director of Twyford Labora- tories Limited. Dr. T. Kennedy has been appointed Chairman and Managing Director of Advita Ltd.Dr. T.J. King is now a Reader in the Department of Organic Chemistry The University Nottingham. Dr. B. P. Mullins formerly the first Head of Chemical Physics Department N.G.T.E. and latterly Head of Chemistry Department of the Royal Air- daft Establishment Farnborough has been pro- moted to Deputy Chief Scientific Officer and appointed Head of the new Chemistry Physics and Metallurgy Department at R.A.E. Mr. M. W. Perrin has been appointed Chairman of the Food Standards Committee for a period of three years from January lst 1963. Dr. B. Robinson of the University Nottingham is Visiting Senior Lecturer in Pharmaceutical Chem- istry at the University of Kumasi Ghana until June 1963. Dr. 0.Stephenson has been appointed Manager of PROCEEDINGS the Chemical Research Department of The British Drug Houses Limited London N.1. Professor A. R. Ubbelohde gave the Second Quin- quennial Van’t Hoff Memorial Lecture of the Royal Netherlands Academy of Sciences and Letters in Amsterdam on October29th 1962 entitled “Transi- tions between Condensed States of Matter.” Mr. L. A. Warwicker formerly with W. and A. Gilbey Limited has taken up an appointment as Quality Controller with Nabisco Foods Limited Welwyn Garden City. Dr. H. Watts Senior Lecturer in Applied Physical Chemistry in the South Australian Institute of Tech- nology will be arriving in the U.K. in January to spend a year on study leave at the University of Reading. Mr. L. A. Whalley formerly with Wareing Brothers and Company Limited has been appointed Lecturer in Chemistry at the City College Norwich.Dr. J. E. Whitley has been appointed Radio- chemist at the Scottish Research Reactor Centre East Kilbride. PROGRAMME OF MEETINGS* JANUARY TO JUNE 1963 Anniversary Meetings 1963 The Anniversary Meetings of the Society will be held in Cardiff on March 26th to 29th 1963. A Programme of the meetings will be sent separately to all Fellows. London Thursday January 17th 1963 at 6 p.m. Centenary Lecture “The Mechanism of the Enzym- ic Decarboxylation of Acetoacetic Acid,” by Professor F. H. Westheimer M.A. Ph.D. To be given in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensington S.W.7. Thursday February 14th at 6 p.m.Centenary Lecture “Problems of Cumulenes and Acid Hydrocarbons,” by Professor Dr. R. Kuhn. To be given in the Lecture Theatre The Royal Institu- tion Albemarle Street W. 1. Thursday February 28th at 6 p.m. Tilden Lecture “The Biosynthesis of Alkaloids,” by Professor A. R. Battersby Ph.D. To be given in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensington s.w.7. Thursday March 14th at 6 p.m. Meeting for the Reading of Original Papers. To be held in the Rooms of the Society Burlington House w.l. Thursday May 9th at 6 p.m. Hugo Muller Lecture “The Biogenesis of Phenolic Alkaloids,” by Professor D. H. R. Barton D.Sc. F.R.S. To be given in the Lecture Theatre The Royal Institution Albemarle Street W.1. Thursday June 6th at 6 p.m. Meeting for the Reading of Original Papers. To be held in the Rooms of the Society Burlington House W.1. herdeen (Joint Meetings with the Royallnstitute of Chemistry and the Society of Chemical Industry to be held in the Medical Physics Lecture Theatre Marischal College.) Tuesday January 22nd 1963 at 8 p.m. Lecture “Soho and Science Scenes from the Eighteenth Century,” by Dr. F. W. Gibbs F.R.I.C. Wednesday February 13th at 8 p.m. Lecture “The Importance of a Quantitative Ap- proach at all Stages in the Development of a Chemical Process,” by A. J. Young. Thursday March 7th at 8 p.m. Lecture “Aromatic Reactivity,” by Professor C. Eaborn D.Sc. F.R.I.C.Aberystwyth (Joint Meetings with the University College of Wales Chemical Society to be held in the Edward Davies Chemical Laboratory.) Thursday January Uth 1963 at 5 p.m. Lecture “New Lamps for Old,” by Dr. W. J. Orville-Thomas. Thursday February 7th at 5 p.m. Lecture “Seeing Molecules with Microwaves,” by Dr. J. Sheridan M.A. * Offprints of this programme can be obtained from the General Secretary The Chemical Society Burlington House, London W.l. DECEMBER 1962 Thursday February 21st at 5 p.m. Lecture “The Active Centres of Enzymes,” by Professor H. N. Rydon D.Sc. F.R.I.C. Thursday March 7th at 5 p.m. Lecture “Nuclear Magnetic Resonance,’’ by Prof- essor E. R. Andrew M.A. Ph.D. Thursday March 14th at 5 p.m. Tilden Lecture “Biosynthesis of Alkaloids,” by Professor A.R.Battersby Ph.D. Birmingham (Joint Meetings with the University Chemical Society to be held in the Chemistry Department The University.) Friday February 8th 1963 at 4.30 p.m. Lecture “Phytol-The Cinderella of Natural Pro- ducts,” by Professor B. C. L. Weedon D.Sc. F.R.I.C. Friday March lst at 4.30 p.m. Lecture “Ionic Polymerisation,” by Professor C. E. H. Bawn C.B.E. Ph.D. F.R.S. Friday May loth at 4.30 p.m. Hugo Miiller Lecture “The Biogenesis of Phenolic Alkaloids,” by Professor D. H. R. Barton D.Sc. F.R.S. Bristol (Joint Meetings with the Royal Institute of Chem- istry and the Society of Chemical Industry to be held in the Department of Chemistry The University un- less otherwise stated.) Thursday January loth 1963 at 6.30 p.m.Lecture “New Developments in Chelatometry,” by Dr. T. S. West F.R.I.C. Thursday January 31st at 6.30 p.m. Jubilee Memorial Lecture “Horizons in Disinfec- tions and Antisepsis,” by G. Sykes M.Sc. F.R.I.C. Thursday February 7th at 6.30 p.m. Lecture “Applications of X-Ray Crystallography in Chemistry,” by H. M. Powell M.A. F.R.S. Tuesday February 19th at 7.30 p.m. Lecture “Luminescence,” by Professor G. F. J. Garlich D.Sc. F.1nst.P. To be given at Gloucester Technical College. Thursday March 7th at 6.30 p.m. Annual Meeting and Lecture “Ceramic Fuels for Nuclear Reactors,” by Dr. J. K. Dawson F.R.I.C. Joint Meeting with the Institute of Fuel. Friday March 22nd.Annual Dinner and Dance. Bristol College of Science and Technology. Cambridge (Joint Meetings with the University Chemical Society to be held in the University Chemical Laboratory Lensfield Road.) Friday February lst 1963 at 8.30 p.m. Lecture “Molecular Shapes and Sizes,” by Dr. L. E. Sutton M.A. F.R.S. Friday February 15th at 8.30 p.m. Centenary Lecture “Problems of Cumulenes and Acid Hydrocarbons,” by Professor Dr. R. Kuhn. Friday March lst at 8.30 p.m. Lecture by Professor R. C. Cookson F.R.I.C. Cardiff (Meetings to be held in the Department of Chem- istry University College Cathays Park unless otherwise stated.) Monday January 21st 1963 at 5 p.m. Lecture “Tetraterpenes,” by Professor B. C. L. Weedon D.Sc. F.R.I.C. Thursday March 21st at 5.30 p.m.Lecture “Stereochemical Factors in Biological Activity,” by Dr. A. H. Beckett F.R.I.C. F.P.S. To be given in the Welsh College of Advanced Tech- nology (Pharmacy Department) Cathays Park. Monday March 25th at 5 p.m. Lecture “Metal Carbonyls and Other Novel Initiators of Polymerisation,” by Professor C. H. Bamford Ph.D. F.R.I.C. Dublin Wednesday March 20th 1963 at 5.30 p.m. Lecture “Recent Developments in Molecular Spectroscopy,” by Dr. H. Rubaclava. To be given in the Department of Chemistry University College. Dundee (Meetings will be held in the Chemistry Department Queen’s College.) Tuesday January 15th 1963 at 5 p.m. Lecture “The Radiation Chemistry of Nitric Oxide and its Implications in Radiobiology,” by Dr.H. C. Sutton. Tuesday February 26th at 5 p.m. Lecture “Some Applications of Nuclear Magnetic Resonance to Organic Chemistry,” by Dr. A. R. Katritzky M.A. Durham (Meetings to be held at The Science Laboratories South Road.) Monday February llth 1963 at 5 p.m. Lecture by Dr. R. E. Richards M.A. F.R.S. Joint Meeting with the Durham Colleges Chemical Society. Monday February 25th at 5 p.m. Tilden Lecture “The Biosynthesis of Alkaloids,” by Professor A. R. Battersby Ph.D. Monday March llth at 5 p.m. Lecture “Some Chemical Aspects of Polymerisation Reactions,” by Professor C. H. Bamford Ph.D. F.R.I.C. Edinburgh Thursday January 17th 1963 at 7.30 p.m. Lecture “The Extrusion of Sulphur from Organic Molecules,” by Dr.J. D. Loudon. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Tuesday January 29th at 4.30 p.m. Lecture “The Bacterial Cell Wall,” by Professor J. Baddiley D.Sc. F.R.S. Joint Meeting with the Uni- versity Chemical Society to be held in the Depart- ment of Chemistry The University. Thursday February 14th at 7.30 p.m. Lecture “Pesticides,” by Dr. R. A. E. Galley F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Thursday February 21st at 4.30 p.m. Official Meeting and Centenary Lecture “Problems of Cumulenes and Acid Hydrocarbons,” by Prof- essor Dr.R. Kuhn. To be given in the Department of Chemistry The University. Tuesday February 26th at 4.30 p.m. Lecture “The Co-ordination Chemistry of Gallium,” by Professor N. N. Greenwood Ph.D. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the Department of Chemistry The University. Thursday March 7th at 7.30 p.m. Lecture “Developments in the Field of Nucleic Acids,” by Professor J. N. Davidson D.Sc. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Exeter Friday March lst 1963 at 5.15 p.m. Lecture “Polysaccharides as Energy Reserves in Plants,” by Professor E. L. Hirst C.B.E. LL.D. F.R.S. To be given in the Washington Singer Laboratories.Glasgow Thursday January 17th 1963 at 4 p.m. Lecture “Carbanions to Carbenes,” by Professor R. N. Haszeldine D.Sc. F.R.I.C. Joint Meeting with the Andersonian Chemical Society to be held at the Royal College of Science and Technology. Thursday February 14th at 4 p.m. Lecture “Substituent Effects in Electrophilic Aro-matic Substitution,” by Professor C. Eaborn D.Sc. PROCEEDINGS F.R.I.C. Joint Meeting with the Alchemists’ Club to be held in the Chemistry Department The Univer- sity. Friday March lst at 4 p.m. Tilden Lecture “The Biosynthesis of Alkaloids,” by Professor A. R. Battersby Ph.D. To be given in the Chemistry Department The Royal College of Science and Technology. Friday March 15th at 4 p.m. Annual General Meeting of Local Fellows followed by Meeting for Reading of Original Papers.To be held in the Chemistry Department The University. Hull Thursday February 28th 1963 at 5 p.m. Lecture “Aromatic Character in 4Membered Rings,” by Dr. J. F. W. McOmie. Joint Meeting with the University Students Chemical Society to be held in the Organic Lecture Theatre The University. Leeds Thursday February 28th 1963 at 5.45 p.m. Lecture “Chemical Basis of the Injury of Cells by Ionising Radiations,” by Dr. P. Alexander. Joint Meeting with the University Union Chemical Society to be held in the Chemistry Lecture Theatre The University. Leicester (Joint Meetings with the University Chemical Society to be held in the Department of Chemistry The University.) Monday February 4th 1963 at 4.30 p.m.Lecture “Recent Studies of Unimolecular Re-actions,” by Professor A. F. Trotman-Dickenson M.A. D.Sc. Tuesday February 19th at 7.30 p.m. Lecture “Chemistry of the Hemicellulose Group,” by Professor E. L. Hirst C.B.E. LL.D. F.R.S. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry. Monday March 4th at 4.30 p.m. Lecture “Addition Accompanying Substitution in Aromatic Systems,” by Professor P. B. D. de la Mare D.Sc. Monday March 18th at 4.30 p.m. Lecture “Degeneracy and Magnetic Resonance Experiments,” by Dr. L. E. Orgel M.A. F.R.S. Liverpool (Joint Meetings with the University Chemical Society to be held in the Donnan Laboratories Chemistry Department The University.) Thursday January 31st 1963 at 5 p.m.Lecture “Carbonium Ion Rearrangements,” by Dr. C. A. Bunton A.R.I.C. DECEMBER 1962 Thursday May 9th,at 5 p.m. Lecture “Magnetism and Stereochemistry of First Row Transition Elements,” by Professor J. Lewis Ph.D. D.Sc. Manchester (Meetings to be held in Room F1 Manchester College of Science and Technology unless otherwise stated.) Thursday January loth 1963 at 6.30 p.m. Lecture “Some Aspects of the Photochemistry of Aromatic Molecules,” by Professor G. Porter Ph.D. F.R.S. Tuesday February Sth at 4.30 p.m. Lecture “Exploring Surface Reactions on the Atomic Scale,” by Dr. J. S. Anderson F.R.S. Joint Meeting with the University of Manchester Faculty of Technology Chemical Society.Thursday February 21st at 6.30 p.m. Lecture “Oxidative Cyclisation,” by Professor G. W. Kenner Sc.D. Thursday March 21st at 6.30 p.m. Lecture “Big Rings,” by Professor R. A. Raphael Ph.D. F.R.S. Thursday April 25th at 10 a.m. Symposium “Chemical Product Development.” Joint Meeting with the Royal Institute of Chemistry the Society of Chemical Industry and the Institute of Petroleum. Place of meeting to be announced. Thursday May 2nd at 6.30 p.m. Hugo Muller Lecture “The Biogenesis of Phenolic Alkaloids,” by Professor D. H. R. Barton D.Sc. F.R.S. Newcastle (Meetings to be held in the Chemistry Department King’s College.) Friday February lst 1963 at 5.30 p.m. Bedson Club Lecture “Chemotherapy and the Organic Chemist,” by Dr.F. L. Rose O.B.E. F.R.S. Monday February 18th at 5.30 p.m. Centenary Lecture “Problems of Cumulenes and Acid Hydrocarbons,” by Professor Dr. R. Kuhn. Tuesday March Sth at 5.30 p.m. Lecture “Some Fast Halogenation Reactions,” by R. P. Bell M.A. F.R.S. Friday March lSth at 5.30 p.m. Lecture “Some New Natural Phenolic Compounds -Structural and Biosynthetic Studies,” by Dr. W. D. Ollis. Northern Ireland Tuesday January 29th 1963 at 7.45 p.m. Centenary Lecture “The Mechanism of the Enzy-matic Decarboxylation of Acetoacetic Acid,” by Professor F. H. Westheimer M.A.. Ph.D. To be given in the Department of Chemistry David Keir Building Queen’s University Belfast. Tuesday May 21st at 4.30 p.m.Lecture “Some Recent Developments in the Chemistry of Polyenes,” by Professor B. C. L. Weedon D.Sc. F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Department of Chemistry David Keir Building Queen’s University Belfast. North Wales (Joint Meetings with the University College of North Wales Chemical Society unless otherwise stated to be held in the Chemistry Department University College Bangor.) Thursday January 31st 1963 at 5.45 p.m. Lecture “Chemical Aspects of Enzyme Specificity,” by Dr. W. J. Whelan F.R.I.C. Thursday February 28th at 5.45 p.m. Lecture “Mass Spectrometry in Chemistry,” by Dr. J. H. Beynon A.R.I.C. Thursday March 14th at 5.45 p.m. Lecture “The Peculiarities of Radical Polymerisa- tion in Solution,” by Professor G.M. Burnett D.Sc. F.R.I.C. Joint Meeting with the Society of Chemical Industry. Thursday May 9th at 5.45 p.m. Lecture “Some Problems Experienced in the Manufacture of Pure Beryllium,” by J. A. Dukes. Nottingham (Joint Meetings with the University Chemical Society to be held in the Chemistry Department The University.) Tuesday January 15th 1963 at 5 p.m. Lecture “Radiocarbon Dating,” by H. Barker. Tuesday January 29th at 5 p.m. Lecture “Biosynthetic Pathways in the Amaryl- lidaceae,” by Professor A. R. Battersby Ph.D. Tuesday February 12th at 5 p.m. Lecture “Tetraterpenes,” by Professor B. C. L. Weedon D.Sc. F.R.I.C. Tuesday March 12th at 5 p.m. Nottingham University Chemical Society.Presiden- tial Address by Dr. T. J. King M.A. Oxford (Joint Meetings with the Alembic Club to be held in the Inorganic Chemistry Laboratory.) Monday February 4th 1963 at 8.30 p.m. Lecture “Infrared Spectra of Surface-adsorbed Molecules,” by Dr. N. Sheppard M.A. Monday February 25th at 8.30 p.m. Lecture “Microcalorimetry of Living procesSes,” by Dr. H. A. Skinner B.A. Monday March 4th at 8.30 p.m. Lecture “The Chemistry of Bacterial Walls and Membranes,” by Professor J. Baddiley D.Sc. F.R.S. Reading (Joint Meetings with the Royal Institute of Chem-istry and the University Chemical Society to be held in the Large Chemistry Lecture Theatre The University.) Wednesday February 6th 1963 at 6 p.m.Lecture “The Study of Bond Properties by Infrared Spectroscopy,” by Dr. L. J. Bellamy. Tuesday March 5th at 6 p.m. Lecture “Molecular Vibrations and Chemical Problems,” by Dr. H. W. Thompson C.B.E. F.R.S. St. Andrews (Joint Meetings with the University Chemical Society to be held in the Chemistry Department St. Salva- tor’s College.) Friday February 8th 1963 at 5.15 p.m. Lecture “The Simplest Chemical Reaction,” by Professor G. Porter Ph.D. F.R.S. Friday February 22nd at 5.15 p.m. Lecture “Some Recent Aspects of Inorganic Fluor- ine Chemistry,” by Dr. D. W. A. Sharp. Joint Meet- ing with the University Chemical Society and the Royal Institute of Chemistry. Friday April 19th at 5.15 p.m. Lecture “Surface Radiochemistry,” by Dr.S. J. Thomson. Friday April 26th at 5.15 p.m. Lecture “Structure Stereochemistry and Biosyn- thesis,” by Professor A. R. Battersby Ph.D. Sheffield (Joint Meetings with the Royal Institute of Chem-istry and the University Chemical Society to be held in the Department of Chemistry The University.) Thursday January 24th 1963 at 4.30 p.m. Lecture “Studies on the Biosynthesis of Ckphalo-sporin C,” by Dr. E. P.Abraham F.R.S. Thursday January 31st at 4.30 p.m. Lecture “The Electronic Spectra of Larger Mole- cules,” by Dr. T. M. Dunn. Thursday February 21st at 7.30 p.m. Lecture “The Way Ahead with D.S.I.R.,” by Sir Harry Melville K.C.B. D.Sc. F.R.S. southampton Friday February 22nd 1963 at 5 p.m. Lecture “Recent Developments in the Measure- PROCEEDINGS ment of Surface Area Adsorption,” by Dr.s. J. Gregg F.R.I.C. Joint Meeting with the Royal Insti-tute of Chemistry to be held in the Department of Chemistry The University. Friday March 8th at 5 p.m. Lecture “The Visible and Infrared Spectra of In- organic Chemistry,” by Dr. T. M. Dunn. Joint Meeting with the Royal Institute of Chemistry to be held in the Department of Chemistry The University. Friday March 8th at 7 p.m. Lecture “Some Aspects of the Chemistry of Fungal Products,” by Dr. C. E. Stickings. To be given at the Portsmouth College of Technology. Wednesday April 3rd at 7 p.m. Lecture “Recent Trends in the Study and Utilisation of Coal,” by A. R. Middleton. To be given at the Portsmouth College of Technology.swansea (Joint Meetings with Student Chemical Society to be held in the Department of Chemistry University College.) Monday February 11 th 1963 at 4.30 p.m. Lecture “Recent Advances in Aromatic Fluorine Chemistry,” by Professor M. Stacey D.Sc. F.R.S. Friday March lst at 4.30 p.m. Lecture “The Place of Kinetics in Chemistry,” by R. P. Bell M.A. F.R.S. Tees-side (Joint Meetings with the Royal Institute of Chem- istry the Society of Chemical Industry and Society for Analytical Chemistry.) Wednesday January 9th 1963 at 8 p.m. Lecture “Explosions and Explosion Research,” by Dr. J. H. Bergoin. To be given at the William Newton School Norton. Friday January 25th at 8 p.m. Lecture “Impressions of Chemistry and Biochem- istry in South America,” by Professor M.Stacey D.Sc. F.R.S. To be given at the William Newton School Norton. Tuesday February 5th at 8 p.m. Lecture “Unusual Properties of Metal Nitrates,” by Professor C. C.Addison D.Sc. F.R.I.C. To be given at the Constantine Technical College. Thursday March 7th at 8 p.m. Lecture “Coal Research,” by Dr. R. R. Gordon. To be given at the Billingham Technical College. Thursday March 14th at 8 p.m. Lecture “The Nature of the Genetic Code,” by Dr. R. J. Watts-Tobin. To be given in the Con- stantine Technical College. DECEMBER 1962 399 OBITUARY NOTICES ALEXANDER GRAHAM FOSTER 1906-1962 ALEXANDER FOSTER, GRAHAM born in London on December 28th 1906 was the only child of Tom Foster a Fleet Street journalist who later became President of the National Union of Journalists.Graham spent his childhood in the London area and entered Dulwich College in 1921. Four years later following matriculation he was awarded an Open Scholarship to St. John’s College Oxford to study under the guidance of Dr. M. P. Appleby. He sat Part I of the Honour School of Natural Science (Chemistry) in 1928 and proceeded to his fourth year of study now under Dr. B. Lambert. This was a memorable and stimulating year for him,culminating in recognition of his academic brilliance by the award in 1929 of his B.Sc. Degree with First Class Honours which was promptly followed by Professor Frederick Soddy’s offer of a Demonstratorship in the Inorganic Chemistry Department.This post was eagerly accepted for already Graham was developing his lasting admiration for life in Oxford and was anxious to make the best use of the research opportunities available to him there. It was a particular pleasure to him that he was in- vited also to undertake tutorial work principally in Inorganic and Physical Chemistry in his own Col- lege. During this period he continued to collaborate with Dr. B. Lambert in researches on gas-solid equi- libria. Two joint papers in the Proceedings of the Royal Society described adsorption of hydroxylic compounds by silica gel and ferric oxide; they heralded Graham’s wide future interest in adsorption processes. In 1932 he obtained a Senior Award froni the Department of Scientific and Industrial Research tenable in Professor A.J. Allmand’s laboratory at King’s College London. Five papers dealing with the sorption of alcohols by ferric oxide and silica gels and with the applicability of the capillary theory reflect his full use of this three-year research appoint- ment for the development of his theories on discon- tinuities in adsorption isothennals. In January 1935 he joined the staff of King’s College as a Demon- strator in Inorganic and Physical Chemistry a temporary appointment for four years only. He par- ticipated in the instruction of students at all stages of their education and had entire charge of the classes for first-year engineering students. Assisted by three postgraduate workers his researches continued to progress but they suffered a severe blow when valuable notes were subsequently destroyed at his home in an air-raid.He left University life in July 1939 to take up a post in the Chemistry Department of Medway Tech-nical College where he stayed for six years. During most of this period he was Acting Head of the Chem- istry Department responsible for the whole of the administration for the general supervision of the laboratories and for the organisation of both day and evening classes in Chemistry and Physics. He served on the County Examinations Board of the Kent Education Committee and held Office as Chairman of the Science Section. His full and varied life at Medway was marred by lack of suitable facilities for his high-vacuum work and he began another line of research involving stabilisation of abnormal valency states with the object of developing new analytical methods.This new trend in his interests led in later years to his work with W.J. Williams on volumetric and gravimetric determinations of cobalt and on the kinetics of the cobalt-catalysed decomposition of hydrogen peroxide. He returned to the University of London in 1945 as Lecturer in Chemistry at Royal Holloway College under Professor T. S. Moore. Later under Professor Gwyn Williams he took charge of the laboratories and practical classes in both Physical and Inorganic Chemistry and was responsible for the main lecture courses to Special Honours students in Thermo- dynamics Surface Chemistry Electrochemistry and Inorganic Chemistry.It was typical of Graham Foster that he did not submit for a higher degree until 1946 when he was awarded his Ph.D. (London); he was always more concerned with current activities than with recognition of earlier achievements. Nevertheless his high academic standing and his un- selfish service to both the College and the University did receive recognition in 1950 with the conferment on him of a Readership in Chemistry of the Univer- sity of London which position he held until his death. Following the death of Professor Gwyn Williams Dr. Foster was Acting Head of the Department until the appointment of Professor E. J. Bourne. Thereafter he continued to assist in administrative matters and in the admission of new students; his sound advice and willing help at all times were most welcome and greatly appreciated.He represented his colleagues on the Academic Board of the College. He returned to his studies of adsorption at Holloway where he carried out the major part of his published work. His own outstanding experimental skills were transmitted to his junior collaborators from whom a high degree of accuracy was demanded. It was in this field that he gained world-wide recogni-tion for his skilful theoretical interpretations of ex- perimental data on hysteresis loops capillary effects multi-molecular adsorption heats of sorption pore size and distribution etc. The magnitude of his untiring efforts to further the cause of Chemistry in the University of London as a whole can perhaps be fully appreciated only by his colleagues in the many component establishments.He gave long service as a member of several Boards of Examiners for B.Sc. Special and B.Sc. General Degrees both Internal and External and he was frequently appointed as an examiner for M.Sc. Ph.D. and D.Sc. Degrees. He was also a Chief Examiner at Advanced and Scholarship Level for the General Certificate of Education (London) ; indeed the teaching of chemistry in schools was always of great concern to him. Appointed to the Board of Studies in Chemistry in 1949 he became its Secretary in 1955 and died in this demanding office. Graham Foster was a really able and successful teacher who appreciated his students’ difficulties and was willing to help them at all times.His lectures were frequently interspersed with humorous asides but he did not refrain from candid comment when PROCEEDINGS the occasion so demanded. To his colleagues he was a loyal friend whose advice was often sought and whose judgment was greatly respected. Even in temperament and generous in character he lubri- cated all our daily activities. He was a he chemist to whom fate could at times have been kinder but of greater consequence he was a balanced man beloved by his fellow men. His wife Patricia whom he married in 1942 was also a chemist having graduated from the University of New Zealand. They had many interests in com-mon including the arts travel in the Mediterranean countries and the cultivation of indoor plants.Together they won several trophies and were active members of The Saintpaulia and Houseplant Society. In recent years Dr. Foster also served on the sub- committee of the University of London Botanical Supply Unit. He died suddenly on May 25th 1962 at Chelsea Flower Show. He left his wife mother and two daughters (Kate 19 and Frances 17) of whom he was always justly proud. Kate is following in her grandfather’s footsteps as a journalist. E. J. BOURNE. JOHN ROBERTSON 1903-1 962 JOHNROBERTSON was born at Stranraer and from the High School there entered the University of Glasgow with which as student and teacher he was associated for the rest of his life. His undergraduate days made a great impression on him spent as they were in the aftermath of a world war and with a strong contingent of ex-Servicemen among his fellow- students.In 1924 he graduated B.Sc. with First Class Honours in Chemistry being among the first to do so under the then New Regulations which specified grades of honours. In the same year he accepted a part-time assistantship and subsequently endured the dreary succession to assistantship and lecture- ship on the staff of the Chemistry Department. Under T. S. Patterson he savoured research in organic chemistry but it never held him in thrall nor although he published several papers was he ever persuaded to submit for a higher degree. His interest was in people and from this stemmed his love of travel his remarkable facility in languages and his absorption professionally in teaching.Earnest and sympathetic yet perpetually youthful from his lively sense of fun he made friends everywhere and no- where more firmly than among his students. They however forgetful of chemistry will always remem- ber their teacher with affection and gratitude. His death in mid-June came suddenly within a few hours of his being taken ill. To his widow and daughter the partners of his happy home-life goes the sympathy of his many friends. J. D. LOUDON. DECEMBER 1962 401 ADDITIONS TO THE LIBRARY Alfred Nobel the man and his work. E. Bergengren. (Translated by A. Blair.) Pp. 222. T. Nelson. London. 1962. (Presented by Nitroglycerine Akteibolaget.) A history of chemistry.J. R. Partington. Vol. 3. Pp. 854. Macmillan. London. 1962. Physical chemistry. A. L. Mee. 6th edn. Pp 719. Heinemann. London. 1962. (Presented by the publisher.) Principles of organic chemistry. T. A. Geissman. 2nd edn. Pp. 854. Freeman. San Francisco. 1962. (Presented by the author.) Applied hydrocarbon thermodynamics. W. C. Ed-mister. Pp. 311. Gulf. Houston Texas. 1961. Syntheses of heterocyclic compounds. Edited by A. L. Mndzhoian. (Translated from the Russian by A. E. Stubbs.) Vol. 3-4 (bound in one volume). Pp. 156. Consultants Bureau. New York. 1960. Structural carbohydrate chemistry. E. G. V. Percival. Revised by E. Percival. Pp.360. J. Garnet Miller. London. 1962. Alkali metal dispersions.I. Fatt and M. Tashima. Pp. 228. Van Nostrand. Princeton N.J. 1961. Chemical analysis the working tool. Edited by C. R. N. Strouts H. N. Wilson and R. T. Parry-Jones. Revised edition of Analytical chemistry. Edited by C. R. N. Strouts et al. 3 Vols. Clarendon Press. Oxford. 1962. (Presented by Imperial Chemical Industries Ltd.) Dunnschicht-Chromatographie.K. Randerath (Mono- graphien zu Angewandte Chemie und Chemie Ingenieur Technik Nr.) Pp.243. Verlag Chemie G.m.b.H. Wein- heim. 1962. (Presented by the publisher.) Principles of titrimetric analysis. E. E. Aynsley and A. B. Littlewood. (R.I.C. Monographs for Teachers No. 6). Pp. 42. Royal Institute of Chemistry. London. 1962. Laboratory planning for chemistry and chemical engineering.Edited by H. F. Lewis. Pp. 522. Reinhold. New York. 1962. Detection and analysis of rare elements. Edited by A. P. Vinogradov and D. I. Ryabchikov. (Translated from the Russian.) Pp 744. Israel Programme for Scientific Translations. Jerusalem. 1962. (Presented by the publisher.) Dust explosions in factories a review of the literature. K. C.Brown and G. J. James. (Safety in Mines Research Establishment Research Report 201 .) Pp.67. S.M.R.E., Ministry of Power. Sheffield. 1962. (Presented by the publisher.) River Pollution 2 Causes and effects. L. Klein. Pp. 456. Butterworths. London. 1962. NEW JOURNALS Annalen der Physik from 1961,7. Review of Coal Tar Technology from 1961,13 No. 2.. 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